Clean by Light Irradiation

Clean by Light Irradiation
Practical Applications of Supported TiO2

Clean by Light Irradiation
Practical Applications of Supported TiO2
Vincenzo Augugliaro, Vittorio Loddo, Giovanni Palmisano and

Leonardo Palmisano
Dipartimento di Ingegneria Chimica dei Processi e dei Materiali, University of
Palermo, Italy
Mario Pagliaro
Istituto per lo Studio dei Materiali Nanostrutturati, CNR, Palermo, Italy
ISBN: 978-1-84755-870-1
A catalogue record for this book is available from the British Library
r V. Augugliaro, V. Loddo, M. Pagliaro, G. Palmisano and L. Palmisano 2010
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Preface
Chemical pollutants are harmful substances for human beings and for the
environment. In water they are in the form of dissolved substances but in air
they can be in the form of particulate, liquid droplets or gases. The con-
taminant species can be classified as primary or secondary pollutants; the
first of these are substances emitted directly from a process, whereas the last
are formed by reaction with primary pollutants. In the case of air pollution,
we must distinguish between outdoor and indoor pollution. Figure P.1 shows
the causes and effects of outdoor air pollution.
The levels of air pollution inside houses are often from two to five times
higher than outdoor levels. There are many sources of indoor air pollution as
household products, including paints, wood preservatives, aerosol sprays,
cleansers and disinfectants, stored fuels and automotive products, hobby sup-
plies and dry-cleaned clothing. Figure P.2 shows the air pollution sources in a
house. Poor indoor air quality is associated with many health problems,
including eye irritation, headaches, allergies and respiratory problems such as
asthma.
Conventional methods of water and air decontamination, even if effective,
are often chemically, energetically and operationally intensive and suitable only
for large systems; moreover, the residuals coming from intensive chemical
treatments can add to the problems of contamination. Advanced oxidation
processes, developed in recent decades, may be used for degradation of pol-
lutants and also for removing pathogens. These methods rely on the formation
of highly reactive chemical species that degrade even the most recalcitrant
molecules.
Among the advanced oxidation processes, photocatalysis in the presence
of an irradiated semiconductor has proven to be very effective in the field
of environment remediation. The use of irradiation to initiate chemical reac-
tions is the principle on which heterogeneous photocatalysis is based; in fact,
the irradiation of a semiconductor oxide with light of suitable energy deter-
mines the production of electron–hole pairs that eventually generate hydroxyl
radicals on the catalyst surface. The radical mechanism of photocatalytic
Clean by Light Irradiation: Practical Applications of Supported TiO2

By Vincenzo Augugliaro, Vittorio Loddo, Mario Pagliaro, Giovanni Palmisano and Leonardo Palmisano
Published by the Royal Society of Chemistry, www.rsc.org
v
vi Preface
CH4 CO2
C
1
SOX
CFC
6
4
2
O3
NOX
Figure P.1 Causes and effects of outdoor air pollution: (1) greenhouse effect, (2)
particulate contamination, (3) increased UV radiation, (4) acid rain, (5)
increased levels of nitrogen oxides and (6) increased ozone concentration.
Paint
Mothballs
Kerosene
Fresh heating
dry cleaning
Curtains
Plywood
Gas
range Fireplace
Wood
stove
Foam padding
Pesticides Asbestos
Disinfectants insulation
Cleaners Radon
Aerosols Heating
Solvents
Glues
Carbon monoxide
Figure P.2 Air pollution sources in a house.

Preface vii
Light Light
VOCs and
Odors Bacteria Germs Fungus
TiO2
Photocatalytic Reaction
Air purification
Deodorization Sterilization
Water purification
Figure P.3 Scheme of photocatalytic remediation.
reactions, which involve fast attack of strongly oxidant radicals, determines

their unselective features. Figure P.3 shows a scheme of photocatalytic
remediation.
The main advantage of heterogeneous photocatalysis, when compared with
conventional methods, is that in most cases it is possible to obtain complete
mineralization of the toxic substrate even in the absence of added reagents. The
role of photocatalyst is therefore that of absorbing radiant energy and trans-
forming it into highly reactive species. An ideal photocatalyst should exhibit the
following features: (i) high reaction rate under band gap (or higher) irradiation;
(ii) photostability; (iii) chemical and biological inactivity; and (iv) ready
availability and low cost. Many semiconductors (such as TiO2, ZnO, ZrO2,
CdS, MoS2, Fe2O3, WO3, etc.), both pure and/or doped, have been examined
and used as photocatalysts for the degradation of environmental pollutants in
air and water. TiO2 has been widely used because it is inexpensive, it is harmless
and its (photo)stability is very high. The use of different types of non-TiO2-
based materials, prepared by means of sophisticated methods, has been pro-
posed by some authors, but it is hard to believe that such materials will find
large-scale environmental applications in the near future, although the possi-
bility of using such materials in a specific niche utilization, for instance in
electronics or in very expensive device, cannot be excluded. Despite the great
research activity developed in last two decades in search for a photocatalyst
with optimal features, titania remains a benchmark against which any alter-
native photocatalyst must be compared.
viii Preface
1200 120
Papers
Patents
1000 100
800 80
600 60
400 40
200 20
0 0
1990 1992 1994 1996 1998 2000 2002 2004 2006 2008
Year
Figure P.4 Number of papers published (’) and patents (E) related to hetero-
geneous photocatalysis by TiO2 since 1990. (Source: Scopus.)
Scientific and industrial interest worldwide in heterogeneous photocatalysis

by TiO2 has increased greatly in recent decades. A clear indicator of this interest
is that the number of papers and patents published in the last two decades has
increased exponentially, as it may be noted from Figure P.4, which reports the
annual number of publications and patents over the last two decades.
TiO2 samples prepared both as powders and films have been characterized
and used for many practical applications. Attention has focused mainly on the
anatase and rutile polymorphs, although some papers reporting the photo-
activity of the brookite phase can be found in the literature. One serious pro-
blem is the difficulty, sometimes, in obtaining pure phases, and the properties
attributed to one phase are due in many cases to a mixture of two or three
phases.
On these grounds this book is focused only on the applications of pure TiO2
supported on various materials. The most popular techniques used to prepare
TiO2-supported materials are also presented together with some specific pre-
parations useful to obtain various TiO2 colloidal dispersions or powders. The
presence of metal and non-metal dopants is neglected, with a few exceptions,
although the authors are well aware of the importance of the presence of for-
eign species in shifting light absorption towards visible region or in slowing
down the recombination rate of the photoproduced electron–hole pairs.
Nevertheless, the use of dopant species is not always beneficial for the photo-
activity; products commercially proposed and/or sold do not contain doped-
TiO2 but, instead, only pure TiO2, generally in the anatase phase.
To satisfactorily understand the working principles of photocatalytic mate-
rials, artifacts and devices presented in this book (which is also aimed at
Preface ix
relatively inexperienced readers), it is important to have knowledge of some of
the fundamentals of heterogeneous photocatalysis. Therefore, Chapter 1
introduces the working principles of the thermodynamic and kinetic of pho-
tocatalytic processes; in this chapter some properties and definitions of semi-
conductors related mainly to TiO2 are reported, together with the peculiarity of
other conductor, insulating and semiconductor materials. Particular attention
is devoted to the surface processes that are important for the occurrence of all
types of kinetic mechanisms. The latter can be explained according to the
Langmuir–Hinshelwood or Eley–Rideal models. Moreover, some studies on
the influence of light intensity on photodegradation rate of the molecules under
investigation are highlighted.
Most of the practical applications of TiO2 imply its deposition in various
ways on different materials. Despite this, it was considered useful to report in
Chapter 2 not only the preparation, characterization and testing of TiO2 films,
mainly on bench scale, but also of powdered crystalline samples with different
particle sizes. The obtainment of TiO2 coated surfaces, in fact, cannot ignore in
many cases the preparation methods of the bare TiO2. Some of the most
popular methods reported are the sol-gel, hydrothermal and solvothermal
methods. As far as films are concerned, few preparation methods can be used
for large-scale film deposition; one method is the magnetron sputtering tech-
nique, due to its low-cost and easy controllability.
Some properties of TiO2 such as its high optical index, refraction and
transparency in the visible wavelength range, and superhydrophilicity allow its
practical application and are reported in Chapter 3. The most important among
them, i.e., the superhydrophilicity exhibited under illumination by suitable
TiO2 thin films supported glasses, for instance, can be invoked to explain why
droplets of water spread completely across the surface during the con-
temporaneous occurrence of a self-cleaning effect. Figure P.5 illustrates these
phenomena.
Chapter 4 deals with the improved performances of various types of TiO2-
supported glasses and their practical uses. Buildings covered with self-cleaning
glasses now exist.
When used in a blend with a concrete structure, TiO2 can decompose organic
and inorganic fouling species, including not only oil, particulates, soot and
grime but also biological organisms and airborne pollutants such as the most
common and harmful volatile organic compounds (VOCs). Chapter 5 describes
the use of cementitious materials, ceramic tiles and various kinds of pavers,
including asphalts TiO2 treated for outdoor and indoor applications.
The preparation of photocatalytic polymers is useful for a wide range of
applications in household appliances, automobile industry, soundproof road
barriers and tents for outdoors applications. Several methods are used to
prepare these materials. Chapter 6 is concerned with TiO2 on plastic, textile,
metal and paper. Indeed, organic matter deposited on textiles coated with a
thin transparent layer of TiO2 can be decomposed, together with smoke smell
and pathogens. Such self-cleaning textiles could be used for sportswear, mili-
tary uniforms and carpets. The field of photocatalytic paper is pioneering and it
x Preface
UV Oil
Light
Water
H H Hydrophilic
Oil Water O O OH group
Ti O Ti O Ti Ti O Ti O Ti
TiO2 TiO2
Figure P.5 Superhydrophilic effect.
is worth noting that the presence of TiO2 also improves the opacity and the
whiteness.
Metals such as stainless steel, aluminium alloy, etc. can be functionalized by
means of TiO2 to gain photocatalytic activity, surface superhydrophilicity and
antibacterial activity.
Heterogeneous photocatalysis is one of the most efficient and cost-effective
air purification technologies and scientists estimate that it could be the main
method of air purification in the near future. This method has attracted the
attention of industry devoted to producing apparatuses for air conditioning,
with the main objective of purifying the indoor air of houses, hospitals,
buildings, farms, etc. Chapter 7 describes not only some devices for air pur-
ification but also some field applications of photocatalytic degradation of
pollutants in water.
Finally, Chapter 8 deals with the most relevant standardization methods
reported in the literature for determining figures of merit in heterogeneous
photocatalysis.
CHAPTER 1
Fundamentals
1.1 Working Principles and Thermodynamics of
Heterogeneous Photocatalysis
1.1.1 Conductors, Insulators and Semiconductors
The valence bond theory is useful in explaining the structure and the geometry
of the molecules but it does not provide direct information on bond energies and
fails to explain the magnetic properties of certain substances. The molecular
orbitals (MO) theory solves these drawbacks. It is based on the assumption that
the electrons of a molecule can be represented by wave functions, c, called
molecular orbitals, characterized by suitable quantic numbers that determine
their form and energy. The combination of two atomic orbitals gives rise to two
molecular orbitals, indicated as c1 and c. If an electron occupies the c1
molecular orbital, a stable bond is formed between two nuclei, and so this is
called bonding orbital. Conversely, when an electron occupies the c orbital it is
called anti-bonding orbital and the presence of an electron promotes the dis-
sociation of the molecule. Molecular orbitals of a solid consisting of n equal
atoms are obtained by means of a linear combination of atomic orbitals. The
number of molecular orbitals formed is equal to that of the atomic ones. By
increasing the number of atoms the difference between the energetic levels
decreases and a continuous band of energy is formed for high values of n.
The width of the various bands and the separation among them depends
on the internuclear equilibrium distance between adjacent atoms. If the
energetic levels of isolated atoms are not so different, progressive enlargement
of the bands may lead to their overlapping by decreasing the internuclear
distance. The most external energetic band full of electrons is called the valence
band (VB).
The energy band model for electrons can be applied to all crystalline solids
and allows one to establish if a substance is a conductive or an insulating
material. Indeed, the properties of a solid are determined by the difference in
energy between the different bands and the distribution of the electrons con-
tained within each band.

1
2 Chapter 1
A B C D
Figure 1.1 Schematic of the energetic bands for conductors, (a) and (b); insulators (c);
and semiconductors (d).
If the valence band is partially filled or it is full and overlapped with a band
of higher energy, electrons can move, allowing conduction (conductors), as in
the case of metals that have relatively few valence electrons that occupy the
lowest levels of the most external band.
In contrast, the valence band is completely filled in ionic or covalent solids
but it is separated by a high energy gap from the subsequent empty band. In
this situation no electrons can move even if high electric fields are applied and
the solid is an insulator. If the forbidden energy gap is not very high, some
electrons could pass into the energetic empty band by means of thermal exci-
tation and the material behaves as a weak conductor, i.e., as a semiconductor.
The empty band, which allows the movement of the electrons, is called the
conduction band (CB).
The energy difference between the lowest conduction band edge and the
highest valence band edge is called the band gap (EG). A material is generally
considered a semiconductor when EGr3 eV, whereas it is considered a wide
band gap semiconductor when its band gap value ranges between 3 and 4 eV.
Figure 1.1 shows the position of the energy bands of different types of
materials.
1.1.2 Properties of Semiconductor Materials

The de Broglie relation1 associates a wavelength with the electron as:
h h
l¼ ¼ ð1:1Þ
p mv
where p is the momentum and h is the Planck constant. It shows that the
wavelength is inversely proportional to the momentum of a particle and that
the frequency is directly proportional to the particle’s kinetic energy:
E
f ¼ ð1:2Þ
h
Fundamentals 3
The wave number corresponds to the number of repeating units of a propa-
gating wave per unit of space. It is defined as:
1
v ¼ ð1:3Þ
l
In the case of non-dispersive waves the wave number is proportional to the

frequency, f:
f
v ¼ ð1:4Þ
v
where v is the propagation velocity of the wave. For electromagnetic waves

propagating in vacuum the following relation is obtained:
f
v ¼ ð1:5Þ
c
where c is the velocity of light.

The wave vector is a vector related to a wave and its amplitude is equal to the
wave number while its direction is that of the propagation of the wave:
2p
k ¼ ð1:6Þ
l
Therefore, the electron momentum can be expressed as:
h

p ¼ hk
¼ ð1:7Þ
l
where h is the reduced Plank constant also known as the Dirac’s constant
(h ¼ h/2p).
The electron energy is therefore:
p2 h2 k2

E¼ ¼ ð1:8Þ
2m 2m
where the coefficient m is the inertial mass of the wave-particle. As m varies with
the wave vector, it is called effective mass, m*, defined as:
h2
m ¼ ð1:9Þ
@2 E=@k2
A semiconductor is called a direct band gap semiconductor if the energy of the

top of the valence band lies below the minimum energy of the conduction band
without a change in momentum, whereas it is called an indirect band gap
4 Chapter 1
Energy
Energy
Band gap
Band gap
Band gap
Difference
in momentum
Momentum Momentum
A B
Figure 1.2 Energy versus momentum for (a) a direct band gap semiconductor and
(b) an indirect band gap semiconductor.
semiconductor if the minimum energy in the conduction band is shifted by a

difference in momentum (Figure 1.2).
The probability f(E) that an energetic level of a solid is occupied by electrons
can be determined by the Fermi–Dirac distribution function.2 It applies to fer-
mions (particles with half-integer spin, including electrons, photons and neu-
trons, which must obey the Pauli exclusion principle) and states that a given
allowed level of energy E is function of temperature and of the Fermi level, E0F,
according to the equation:
1
f ðEÞ ¼ ð1:10Þ
EE 0
1 þ exp kB TF
where kB is the Boltzmann constant. The level E0F represents the probability of
50% of finding an electron in it. For intrinsic semiconductors and for insulating
materials, E0F falls inside the energetic gap and its value depends on the effective
mass of electrons present at the end of the conduction band (m*e), on the
effective mass of electrons at the beginning of the valence band (m*h), and on the
amplitude of the band gap (EG) according to the following equation:
mh
EF0 ¼ 12EG þ 34kT ln ð1:11Þ
me
The value of E0F is equivalent to the electrochemical potential of the electron,

i.e., it can be considered as the work necessary to transport an electron from an
infinite distance to the semiconductor.
Figure 1.3 shows that the Fermi–Dirac distribution is a step function at
T ¼ 0 K. It has the value of 1 and 0 for energies below and above the Fermi
level, respectively. As the temperature increases above T ¼ 0 K, the distribution
of electrons in a material changes. At T40 K the probability that energy levels
Fundamentals 5
f(E)
T2>T1
1 T1 > 0 K
T=0K
0.5
0
E0F E
Figure 1.3 Fermi–Dirac distribution for several temperatures.
above E0F are occupied, and similarly energy levels below E0F are empty, is not
zero. Moreover, the probability that an energy level above E0F is occupied
increases with temperature (distribution sigmoidal in shape) because some
electrons begin to be thermally excited to energy levels above the chemical
potential, m(E0F). To understand the meaning of the chemical potential some
considerations are presented here.
In determining the surface composition it is important to consider the
thermodynamics of surfaces. The surface contribution to the free energy, G, of
a solid is always positive. To create a new surface, it is necessary to perform a
work on the system, which is employed to break bonds between the surface
atoms. The work required to increase the surface area by dA, by means of a
reversible path, at constant temperature and pressure, depends on the surface
tension g according to the following relation:
dWP;T ¼ g dA ð1:12Þ
For a single-component system, it is possible to express g as a function of the
surface free energy per unit area, GS, as:
S
S @G
g¼G þA ð1:13Þ
@A P;T
where GS represents the work (per unit surface) done to form a new surface dA
and the second term of the right-hand side is the work done in stretching a pre-
existent surface to increase it by dA. In this last case the number of surface
atoms is fixed, whereas the state of strain of the surface changes. If the surface is
unstrained, the second term of the right-hand side of Equation (1.13) is zero
and g is equal to the surface free energy:

S @G
g¼G ¼ ð1:14Þ
@A P;T
6 Chapter 1
For a multicomponent system the Gibbs equation can be written as:
X
dg ¼ SS dT Gi dmi ð1:15Þ
i
were SS is the surface entropy, mi the chemical potential of species i, and Gi is the
number of moles of component i per unit surface (nSi /A) in excess with respect
to those that would be present if the system was homogeneous from bulk up to
the surface.
The chemical potential can be expressed as:
mi ¼ m0i þ RT ln xi ð1:16Þ
where m0i is the standard chemical potential of the pure component i.

By substituting Equation (1.16) in Equation (1.15), at constant temperature,
the following relation is obtained:

1 @g
Gi ¼ ð1:17Þ
RT @ ln xi P;T;mj6¼i
From Equation (1.17) it is possible to determine the excess concentration of a

component by taking the derivative of the surface tension with respect to its
concentration in the bulk.
Equation (1.17) states that if the surface tension decreases by increasing the
bulk concentration of a component, the component will have a greater surface
concentration (Gi40). Moreover, the component with the lowest surface ten-
sion will form a surface layer (if the temperature is high enough to allow its
diffusion).
Owing to the difficulty in measuring the surface tension of the solids, the
above equations allow us to determine the surface composition only qualita-
tively; to obtain more precise data it is necessary to apply statistic thermo-
dynamics and experimental techniques.
Some types of impurities and imperfections may drastically affect the electric
properties of a semiconductor. In fact the conductivity of a semiconductor can
be significantly increased by adding foreign atoms in the lattice (doping) that
make electrons available in the conduction band and holes available in the
valence band. For example, silicon has a crystal structure similar to that of
diamond (Figure 1.4) and each silicon atom forms four covalent bonds with
four nearest atoms, corresponding to a chemical valence equal to four. The
addition of atoms, for instance arsenic, phosphorous or antimony, having one
valence electron more will lead to an excess of positive charge (Figure 1.5a), due
to the transfer of an electron from the foreign atom to the conduction band
(donor doping).
If the foreign atom, for instance boron, gallium, indium, has one valence
electron less it can accept one electron from the valence band (acceptor doping)
(Figure 1.5b). In the first case (Figure 1.5a) an energetic level close to the
Fundamentals 7
Figure 1.4 Crystal structure of silicon.
Figure 1.5 (a) With an arsenic impurity, silicon has an electron available for con-
duction; (b) with a boron impurity, silicon has a positive hole available.
8 Chapter 1
conduction band is introduced; consequently, electrons can pass more easily in
it. In this case the solid is called an ‘‘n’’ type semiconductor and the Fermi level
will be close to the conduction band (Figure 1.6b). In the second case an
energetic level close to the valence band is formed, in which electrons can be
promoted with the formation of holes. Here, the semiconductor is of ‘‘p’’ type
and its Fermi level will be close to the valence band (Figure 1.6c).
The notion of energetic levels of electrons in solids can be extended to the case
of an electrolytic solution containing a redox system.3 The occupied electronic
levels correspond to the energetic states of the reduced species whereas the
unoccupied ones correspond to the energetic states of the oxidized species. The
Fermi level of the redox couple, EF,redox, corresponds to the electrochemical
potential of electrons in the redox system and it is equivalent to the reduction
potential, V0. To correlate the energetic levels of a semiconductor to those of a
redox couple in an electrolyte, two different scales can be used. The first is
expressed in eV, and the other in V (Figure 1.7a). The two scales differ because
in solid-state physics zero is the level of an electron in a vacuum, whereas in
electrochemistry the reference is the potential of the normal hydrogen electrode
EC EC EC
E (eV) EF E (eV) EF E (eV) EF
EV EV EV
(a) (b) (c)
Figure 1.6 Energetic levels of a semiconductor: (a) intrinsic semiconductor; (b) ‘‘n’’
type semiconductor; (c) ‘‘p’’ type semiconductor.
E (eV)
Semiconductor Electrolyte
0
EC
(H+/H2) -4.5 EF 0.0 (H+/H2)

EF,redox
V0,redox
EV
E (V)
(a)
EC
EF,redox
EF
EV
(b)
Figure 1.7 Formation of a junction between an ‘‘n’’ type semiconductor and a

solution: (a) before contact and (b) at equilibrium.
Fundamentals 9
(NHE). The two scales can be correlated using the potential of NHE, which is
equal to 4.5 eV when it is referred to that of the electron in vacuum.4
If a semiconductor is placed in contact with a solution containing a redox
couple, equilibrium is reached when the Fermi levels of both phases become
equal. This occurs by means of an electron exchange from solid and electrolyte,
which leads to the generation of a charge inside the semiconductor. This charge
is distributed in a spatial charge region near the surface, in which the values of
holes and electrons concentrations also differ considerably from those inside
the semiconductor. Figure 1.7(a) shows schematically the energetic levels of a
‘‘n’’ type semiconductor and a redox electrolyte before contact. In particular, as
the energy of the Fermi level is higher than that of the electrolyte, equilibrium is
reached by electron transfer from the semiconductor to the solution. The
electric field produced by this transfer is represented by the upward band
bending (Figure 1.7b). Owing to the presence of the field, holes in excess gen-
erated in the spatial charge region move toward the semiconductor surface,
whereas electrons in excess migrate from the surface to the bulk of the solid.
Figure 1.8 shows the contact between a redox electrolyte and a ‘‘p’’ type
semiconductor. In this case transfer of electrons occurs from the electrolyte to
the semiconductor and the band bending is downward.
If the potential of the electrode changes due to an anodic or cathodic
polarization, a shift of the Fermi level of the semiconductor with respect to that
of the solution occurs with an opposite curvature of the bands (Figure 1.9).
For a particular value of the electrode potential, the charge excess disappears
and the bands become flat from the bulk to the surface of the semiconductor.
The corresponding potential is called the flat band potential, VFB, and the
determination of this potential allows us to calculate the values of the energy of
the conduction and the valence bands.5
E (eV)
Semiconductor Electrolyte
0
EC
(H+/H2) -4.5 EF EF,redox 0.0 (H+/H2)

V0,redox
EV
E (V)
(a)
EC
EF,redox
EF
EV
(b)
Figure 1.8 Formation of a junction between a ‘‘p’’ type semiconductor and a solu-
tion: (a) before contact and (b) at equilibrium.
10 Chapter 1
EC
EC ΔV VFB
EF
EF,redox EF,redox
EF
EV
EV E (V) E (V)
(a) (b)
Figure 1.9 Scheme of the energetic levels at the interface semiconductor–electrolyte for
an ‘‘n’’ type semiconductor: (a) at equilibrium and (b) flat band potential.
hν
EC -
EF,redox
EF
EV
(a) +
EC - hν
EF,redox
EF
EV
+
(b)
Figure 1.10 Generation of electron–hole pair due to irradiation of (a) an ‘‘n’’ type
semiconductor and (b) a ‘‘p’’ type semiconductor.
When a semiconductor is irradiated by radiation of suitable energy – equal to

or higher than that of the band gap, EG – electrons can be promoted from the
valence band to the conduction band. Figure 1.10 shows the scheme of elec-
tron–hole pair formation due to the absorption of a photon by the
semiconductor.
The existence of an electric field in the spatial charge region allows the
separation of the photogenerated pairs. In the case of ‘‘n’’ type semiconduc-
tors, electrons migrate toward the bulk whereas holes move to the surface
(Figure 1.10a). In the case of ‘‘p’’ semiconductors, holes move toward the bulk
whereas electrons move to the surface (Figure 1.10b).
Photoproduced holes and electrons, during their migration in opposite
directions, can (i) recombine and dissipate their energy as either electro-
magnetic radiation (photon emission) or more simply as heat, or (ii) react with
electron-acceptor or electron-donor species present at the semiconductor–
electrolyte interface, thereby reducing or oxidizing them, respectively.
The energy of the conduction band edge, EC, corresponds to the potential of
the photogenerated electrons, whereas the energy of the valence band edge, EV,
Fundamentals 11
Ox2 Ox2
CB CB CB CB
Ox2 Ox2
Red1 Red1
VB VB VB VB
Red1 Red1
(a) (b) (c) (d) E (V)
Figure 1.11 Relative positions of the valence and conduction bands and the energies
of two redox couples. Only for case (d) are both reduction and oxidation
reactions thermodynamically allowed. Ox2 and Red1 represent the oxi-
dized and reduced species, respectively, of two different redox couples.
corresponds to the potential of the holes. If EC is more negative than the

potential of a species present in solution, electrons reaching the interface can
reduce the oxidized form of the redox couple. Conversely, if the potential of EV
is more positive than that of the redox couple, photoproduced holes can oxidize
its reduced form (Figure 1.11). Knowledge of the relative edge positions of the
bands and of the energetic levels of the redox couples is essential to establish if
thermodynamics allow the occurrence of oxidation and/or reduction of the
species in solution.
Figure 1.12 reports the band gaps and the positions of the valence band and
conduction band edges for various semiconductors.
1.1.3 Photocatalytic Processes

The photocatalytic properties of a semiconductor depend on the position of the
energetic levels, on the mobility and mean lifetime of the photogenerated
electrons and holes, on the light absorption coefficient and on the nature of the
interface. Moreover, the photoactivity depends on the methods of preparation
of the powders, which allows us to vary many physicochemical properties of the
semiconductor by controlling the crystalline structure, the surface area and the
particle size distribution.
In a photocatalytic system the behavior of each single particle of semi-
conductor is similar to that of a photoelectrochemical cell constituted by a
semiconductor electrode in contact with an electrode of an inert metal.6 In a
photoelectrochemical cell an oxidation or reduction reaction may occur on the
semiconductor electrode, whereas in a semiconductor particle immersed in an
electrolyte solution both reactions occur simultaneously by hole transfer
from the valence band and by electron transfer from the conduction band
(Figure 1.13).
12 Chapter 1
E (eV)
-2.0
ZnS
-1.0 CdS CdTe CdSe

SrTiO3 Si
TiO2
MoS2
0.0 WO3 Fe2O3
1.4 1.1
3.6 2.4 1.7 1.75
3.0
3.2
1.0
2.3
2.0 2.8
3.0
Figure 1.12 Positions of the band edges for some semiconductors in contact with
aqueous electrolyte at pH 0.
Ox1 Red1
- CB
hν
VB
+
Red2 Ox2
Figure 1.13 Scheme of the photocatalytic process occurring on an illuminated par-

ticle in contact with a redox system. The oxidizing agent Ox1 is oxygen
and the reducing agent is an organic substrate.
An advantage in using semiconductor powder suspensions lies in the fact

that each particle acts as a small photocell, and in 100 mg of powder, consisting
for example of 0.1 mm diameter particles, more than 1011 independent particles
are present.
Generally, the powders have large surface areas (1–100 m2 g1), which favors
the occurrence of charge transfer reactions at the interface between the semi-
conductor surface and the redox electrolyte.
Separation of the electron–hole pairs increases with increasing thickness of
the spatial charge region, which depends on the doping of the semiconductor.
When the volume of the particles decreases, the effect on charge separation
Fundamentals 13
becomes a minimum as, sometimes, the particle size is smaller than the thick-
ness of the spatial charge region. The absorption of radiation of suitable
wavelength by the semiconductor allows the transformation of light into che-
mical energy; this phenomenon represents a fundamental step in heterogeneous
photocatalysis. In particular, when aqueous suspensions of semiconductor
powders are irradiated, at the solid–liquid interface a great variety of photo-
induced chemical reactions, able to degrade many organic and inorganic
molecules, can occur by means of formation of very reactive radical species that
are generated in the presence of O2 and H2O. The following scheme shows the
events that can occur at the semiconductor–water interface when TiO2 is used
as the photocatalyst:

þ
TiO2 þ hn ! TiO2 e
ðCBÞ þ hðVBÞ ð1:18Þ
OH þ hþ
ðVBÞ ! OH ð1:19Þ

O 2 þ e
ðCBÞ ! O2 ð1:20Þ

O þ
2 þ H ! HO2 ð1:21Þ
2 HO2 ! O2 þ H2 O2 ð1:22Þ
H2 O2 þ O
2 ! OH þ OH þ O2 ð1:23Þ
The photocatalytic method allows, moreover, the elimination of many inor-

ganic ionic pollutants present in water by either reducing them to their ele-
mental form on the surface of the catalyst particle:

Mnþ
ðaqÞ þ neðCBÞ ! MðsurfÞ ð1:24Þ
or transforming them into less noxious species. For example, the reduction of
Cr(VI) to Cr(III) allows the elimination of chromium by means of its subsequent
precipitation as hydroxide.
The deposition of small amounts of noble metals on the particle surface of a
semiconductor can be used to increase its photoactivity. Indeed, the photo-
oxidation rate of organic compounds is generally limited by the rate of transfer
of electrons to oxygen adsorbed on the semiconductor surface. The more
electrons there are available to reduce oxygen, the higher the reaction rate.
It is possible to explain the effect of the presence of a noble metal by com-
paring a photoelectrochemical cell and a process occurring by irradiating an ‘‘n’’
type semiconductor particle partially covered with ‘‘islands’’ of Pt (Figure 1.14).
The photocatalytic activity of a semiconductor powder is based on oxidation
and reduction processes that occur continuously on different zones of the same
particle. In the presence of metals such as Au, Ag, Pd and Pt physically
separated reaction sites for the photogenerated pairs exist, similarly to a cell
consisting of a ‘‘n’’ type semiconductor and a platinum counter-electrode, in
14 Chapter 1
Pt
hν hν
n-SC
n-SC Pt
e
Pt n-SC
A- A- e
e e -
-
- A -
A
D+ D+
Pt D
D
+ +
n-SC
(a) (b)
Figure 1.14 Photocatalytic processes in a photoelectrochemical cell (a) and on an

irradiated ‘‘n’’ type semiconductor particle covered with ‘‘islands’’ of
platinum (b).
which the reduction of oxidized species occurs on the metallic electrode whereas
oxidation of the reduced species occurs on the semiconductor.
In the modified particles the photogenerated electrons are transferred onto
the metallic islands whereas the holes remain on the semiconductor; this results
in an acceleration of the process kinetics, due to the decrease in electron–hole
recombination rate.
The same beneficial effect can be obtained by partially covering the particle
surface with oxides such as RuO2 or NiO.7
Another way to realize efficient electron–hole pair separation is to use
mixtures of two different semiconductor powders, such as CdS and TiO28 or
WO3 and WS2.9
The coupling of two semiconductors with different energies for the valence
and conduction bands allows the vectorial transfer of electrons and holes from
one semiconductor to the other, thereby decreasing the probability of their
recombination and increasing the efficiency of the charge-transfer process at the
semiconductor–electrolyte interface.
Figure 1.15 sketches the transfer of electrons from the more cathodic con-
duction band of a semiconductor to that of another one, and the con-
temporaneous transfer of holes from the more anodic valence band of the
second semiconductor to the valence band of the first one:

SC1 e þ hþ þ SC2 e þ hþ ! SC1 hþ þ hþ þ SC2 ðe þ e Þ ð1:25Þ
Fundamentals 15
Ox2
-
-
Red1
hν'
hν
Ox1 +
+
Red2 SC2
V SC1
SC1 = CdS; WS2 SC2 = TiO2; WS3
Figure 1.15 Scheme of the charge-transfer processes that occur on two coupled
semiconductors.
In the case of CdS and TiO2 holes in excess in CdS can oxidize the organic
substrate, whereas electrons in excess in TiO2 can react with the adsorbed
molecular oxygen.8
Depending on the type of photocatalyst used, different reactions can take
place with the substrate to be degraded. Clearly, the employed photocatalyst
must satisfy some requirements that allow a practical convenient use. First, its
absorption spectrum must include radiations in the near-UV region and pos-
sibly also in a part of the visible region. Second, it must be a common, (pho-
to)stable and not costly compound that can be reused. Finally, the energy
associated with the valence band, EV, must allow the formation of species able
to oxidize most organic molecules and the recombination rate of electrons and
holes should be relatively low so that the photogenerated charges can migrate
to its surface and give rise to redox processes with appreciable rate.
The semiconductor most frequently used is, undoubtedly, titanium dioxide,
which is produced in large amounts as a low cost pigment. The photocatalytic
activity of anatase, rutile and brookite polymorphic modifications of TiO2 is
affected by several factors such as the crystalline structure, the surface area, the
particle size distribution and the density of surface hydroxyl groups. Although
the positions of valence and conduction bands of both anatase and rutile are
positive enough to allow the oxidation of many organic molecules, the anatase
phase shows a higher activity as the level of its conduction band is more
favorable for the electron transfer needed for the complementary reduction
reaction. The poor efficiency of rutile is due mainly to the high recombination
rate of electron–hole pairs and to its low ability to photoadsorb oxygen.10
It can be taken into account, however, that the most common TiO2 photo-
catalysts, e.g., Degussa P25 (ca. 80% anatase, 20% rutile), contain a mixture of
both crystalline modifications.
The high band gap for anatase (EG ¼ 3.2 eV) and rutile (EG ¼ 3.0 eV) phases
allows us to utilize only radiations with a wavelength lower than ca. 400 nm,
which represents ca. 5% of solar light. A method to increase light absorption
in the visible region is to dope TiO2 by the addition of transition metal ions.
16 Chapter 1
The presence of these dopants introduces energetic levels in the band gap of
TiO2, thus allowing the absorption of visible radiation. This effect is particu-
larly important for powders containing chromium species, which shift light
absorption towards the red end of the spectrum.11–14
The photocatalytic activity of doped powders is generally lower than that of
bare TiO2, with the exception of samples containing W or Mo in concentrations
lower than 1%. The negative effect is due to an increase in the recombination
rate of electron–hole pairs and/or a decrease of the free diffusion mean path
length of the charge carriers. The higher photoactivity found in the presence of
W and Mo can be attributed to a lower recombination rate due to redox
processes leading to trapping of photoproduced electrons through the forma-
tion of W(V) or Mo(V) species, from which, successively, the electrons are
transferred to oxygen molecules.15,16
1.2 Kinetics of Photocatalytic Processes

Heterogeneous photocatalytic reactions should be studied by following the
same methodology used for heterogeneous catalytic reactions and similar
problems must be overcome.
In catalysis the reaction is accelerated by the presence of small amounts
of a particular substance called a catalyst. One of the fundamental principles
of catalysis is that of catalytic cycle based on the definition of catalysis by
Boudart: ‘‘A catalyst is a substance that transforms reactants into products,
through an uninterrupted and repeated cycle of elementary steps in which the
catalyst is changed through a sequence of reactive intermediates, until the last
step in the cycle regenerates the catalyst in its original form.’’ Heterogeneous
catalysis involves systems in which reactants and catalyst are physically sepa-
rated phases.
Photocatalysis is a ‘‘change in the rate of a chemical reaction or its gen-
eration under the action of ultraviolet, visible or infrared radiation in the
presence of a substance – the photocatalyst – that absorbs light and is involved
in the chemical transformations of the reaction partners.’’ Then a photocatalyst
is a ‘‘substance able to produce, by absorption of ultraviolet, visible, or infrared
radiation, chemical transformations of the reaction partners, repeatedly com-
ing with them into intermediate chemical interactions and regenerating its
chemical composition after each cycle of such interactions.’’
The definition of heterogeneous catalysis implies that at least one reactant
remains attached for a significant time on the surface of a solid catalyst.
When a fresh clean surface is exposed to a fluid, the molecules of the fluid or
those dissolved in it will concentrate preferentially on the surface: this phe-
nomenon is called ‘‘adsorption.’’17 The extent of the interactions of these
molecules (adsorbate) with the solid (adsorbent) may vary widely for the var-
ious systems and it is possible to distinguish two main types of adsorption:
physical adsorption and chemisorption. Physical adsorption is due to forces of
molecular (van der Waals) interactions such as for instance attractions between
Fundamentals 17
permanent or induced dipole and quadrupole. Therefore, physical adsorption
can be considered as the condensation of a vapor to form a liquid or the
liquefaction of a gas on the solid surface.
Chemisorption is due to a rearrangement of electrons of both the fluid and
the surface with the consequent formation of chemical bonds. It is possible to
distinguish between the two types of adsorption by measuring the ‘‘heat of
adsorption.’’ The heat exchanged per mole of gas adsorbed generally ranges
between 2 and 6 kcal for physical adsorption (but values as large as 20 kcal have
been reported) whereas chemisorption can involve a few hundred kcal per mole
(rarely are values below 20 kcal found). The amount of fluid adsorbed and the
adsorption–desorption equilibrium depends on the nature of the adsorbent and
of the adsorbate and also on the pressure and the temperature. The specific
surface area of the solid adsorbent, of course, is a parameter of paramount
importance. The most convenient method for defining an adsorption equili-
brium is by analysis of the ‘‘adsorption isotherms.’’ An adsorption isotherm
shows the influence of the equilibrium pressure upon the amount of adsorbed
gas at constant temperature. Isotherms derived both theoretically and experi-
mentally can be represented by simple equations that correlate directly the
concentration of the adsorbed species to the pressure. A selection of adsorption
isotherms generally used in various kinetic interpretations of surface reactions
is reported here:
V bP
¼y¼ Langmuir ð1:26Þ
Vm 1 þ bP
V ¼ k P1=n ; n41 Freundlich ð1:27Þ
V 1
¼ y ¼ ln c0 P Temkin ð1:28Þ
Vm a
where V is the volume adsorbed, Vm the volume required to form a monolayer

on the adsorbent surface, y is the fraction of monolayer covered at the equi-
librium pressure P, and a, b, k and c0 are constants.
Photocatalysis on wide band gap solids (EG Z 3 eV) is related to photo-
physical processes that transform under irradiation the surface of the solid, on
which ‘‘photoadsorption and/or photodesorption’’ phenomena can occur.
Photocatalysis taking place at the boundaries between two phases can be
expressed symbolically as:
hn
A ! B ð1:29Þ
Cat
were A and B are the reactant and product, respectively, and Cat is the solid
photocatalyst.
Photoadsorption is defined as ‘‘adsorption, typically chemisorption, initiated
by ultraviolet, visible, or infrared radiation either by the adsorbate or by the
18 Chapter 1
adsorbent.’’ It can be represented as:
hn
A ! Aads ð1:30Þ
Cat
were A is the adsorbate molecule and Aads represents the photoadsorbed spe-
cies. Photoadsorption can be seen as the first step of ‘‘photoexcitation’’ of a
heterogeneous system, i.e., the act by which an excited state is produced in a
molecule or solid catalyst by absorption of UV, Vis or infrared radiation.
For gas–solid and liquid–solid systems the interaction of a species with the
solid surface depends on the chemical nature of the species and on the chemical
and physical nature of the solid. For non-illuminated surfaces of semi-
conductor oxides a thermodynamic equilibrium between a species and the solid
is established only when the electrochemical potential of the electrons in the
entire system is uniform. When the adsorption–desorption equilibrium is
established, an aliquot of the species is located in an adsorbed layer, held at the
surface by either weak or strong bonding forces.
When a photocatalyst goes from dark conditions to irradiated ones, the
radiation absorption causes its surface to undergo the series of changes needed
to eventually allow the occurrence of photoprocesses.18,19 Essentially, the
interaction of a photon with a solid semiconductor gives rise to an increase of
the vibrational state of the lattice or the number of quasi-free charge carriers,
i.e., it generates an excited state of the solid. Illumination with band gap or
greater energy creates a perturbation to this adsorption–desorption equilibrium
established in the dark; under irradiation, the previous equilibrium is displaced,
determining a net photoadsorption or photodesorption of species. A new
equilibrium is achieved when the species and the solid acquire the same elec-
trochemical potential.18,19
Direct observation of photosorption phenomena at the TiO2 surface has
been reported in several earlier studies, focusing on the role played by surface
OH groups in the photoadsorption of oxygen and therefore in regulating the
TiO2 photoactivity. For example, UV illumination stimulates desorption of
oxygen and water molecules adsorbed at the TiO2 surface20–24 while studies by
IR and XPS reveal that the amount of OH groups on the TiO2 surface increases
upon UV illumination.25–29 These changes are generally fast and reversible, i.e.,
once irradiation is stopped the surface recovers its previous features, under
equal initial conditions. A well-recognized indication that irradiation modifies
the surface of wide band gap solids is the post-sorption or memory effect, i.e.,
the adsorption in the dark caused by pre-irradiation of the solid surface.30,31
More recent and clear evidence of this behavior is the phenomenon of
induced superhydrophilicity, i.e., the generation of a highly hydrophilic TiO2
surface by UV illumination.22,32–37 The superhydrophilic property of the TiO2
surface allows water to spread completely across the surface rather than
remaining as droplets. For a film that consists of only TiO2, the contact angle of
water almost becomes zero during UV irradiation. However, the contact angle
increases and is restored comparatively quickly in the dark. One of the most
Fundamentals 19
interesting aspects of TiO2 is that photocatalysis and induced hydrophilicity
can take place simultaneously on the same surface even though the mechanisms
are different. In the case of photocatalysis UV light excites the catalyst and
pairs of electrons and holes are generated; the photogenerated electrons then
react with molecular oxygen to produce superoxide radical anions and the
photogenerated holes react with water to produce hydroxyl radicals. These two
types of radicals work to carry out redox reactions with species adsorbed on the
TiO2 surface. On the other hand, surface hydroxyl groups can trap photo-
generated holes and improve the separation of electrons and holes, which
results in enhancement of photocatalysis.
Chapter 3 gives a more detailed explanation of superhydrophilicity.
For liquid–solid systems, adsorption phenomena involving ions occur with a
transfer of electric charge, causing a significant variation of the electronic band
structure of the surface. The charge transfer is responsible for the formation of
the so-called space-charge layer where the potential difference between surface
and bulk creates an electric field that can play a beneficial role in further
adsorption steps. Most photons are absorbed in the superficial layer of the solid
where the space-charge exists and the photoelectrons straightforwardly interact
with the electric field present there. The consequence is a more efficient
separation of the electrons and holes within the space-charge layer, i.e., an
increase of their mean lifetime.
Photoadsorbed species can act (i) as surface-hole trapping and photoelec-
trons can be trapped in the bulk of the solid or (ii) as surface-electron trapping;
in the latter case holes can react with OH surface groups and/or H2O. Both
alternatives depend on the chemical nature of the molecule to be adsorbed and
on the type of the solid adsorbent. Notably, in the gas–solid regime only gas-
eous species or lattice ions can be involved, whereas in the liquid phase the
interaction with the solvent should also be considered.
All the above considerations allow us to conclude that the electronic surface
modifications created under irradiation eventually induce photoadsorption
both in gas–solid and in liquid–solid regimes, which are the photoadsorption
phenomena strictly related to the photoactivity of the solid photocatalysts.
When the light source is switched off, a reversal of the process could occur,
although reversibility is rarely complete and the achievement of a new equili-
brium depends mainly on kinetics rather than thermodynamic factors.
Photoexcitation of a semiconductor solid is a quite complicated process.
Indeed, the absorption of photons is strictly correlated with the nature of the
crystal sites, which can be regular or with imperfections such as intrinsic and
extrinsic lattice defects. It is possible to distinguish four simplified types of
electronic excitations induced by light absorption. In a perfect lattice absorp-
tion can produce only intrinsic photoexcitations with (i) the promotion of
electrons from the valence band to the conduction band with formation of free
electron–hole pairs (separated electrons and holes); (ii) the formation of free
bulk excitons (the combination of an electron and a positive hole that is free to
move through a non-metallic crystal as a unit). In an imperfect lattice the
presence of defects causes extrinsic absorption of light, in particular (iii) photon
20 Chapter 1
Mgas Mgas
surface (c’)
(M-+M+)s
Ms
(d’) (e’)
hν2
(a’) Ls, Ds (e-+h+, e0)s (S-+S+)
(e) (b’)
bulk
hν1 (c)
(a) Lb (e-+h+, e0)b (F, V)b
hν 2
hν3
Db (d)
(b) Q
Figure 1.16 Photo-induced processes in a heterogeneous system containing a wide

band gap semiconductor.
absorption by defects generating electronically excited defects and bound and/

or self-trapped excitons; (iv) photon absorption generating ionization of defects
(transitions between localized and delocalized electronic states).
The scheme of Figure 1.16 shows in detail the processes described above. It is
possible to distinguish bulk and surface processes.38,39
Intrinsic photoexcitation of the lattice, Lb, [(a) in Figure 1.16] occurs by the
fundamental absorption of photons of light with energy higher or equal to that
of the band gap (hn1 Z EG) and the consequent formation of free electrons (e)
and holes (h1), or excitons (e0) that can recombine (band to band recombi-
nation of free charge carriers).
Pre-existing bulk defects (Db) can lead to an extrinsic photoexcitation (b) by
light with energy hn2ohn1, with the formation of free electrons and holes. The
reverse process is the recombination and exciton decay through defects.
Another bulk process is the trapping of free charge carriers and excitons by
bulk defects (c) to form color centers or deep traps (F-type: vacancies occupied
by electrons, and V-type: vacancies occupied by holes). Photobleaching (hn3) or
thermo-annealing of color centers (d) affords free electrons and holes.
As far as the surface processes are concerned, light absorption (hn2) by
regular, Ls, and irregular, Ds, surface states (a 0 ) yields free charge carriers and
excitons. Their surface recombination is likely to be accompanied by lumi-
nescence, whereas their trapping by surface defects, S, (b 0 ) yields surface active
centers (S and S1) for adsorption and catalysis.
Adsorption of molecules in the gas or liquid phase (c 0 ) generates adsorption–
desorption equilibria on the solid surface. The interaction of surface charge car-
riers and excitons with the adsorbed molecules (d 0 ) can promote surface chemical
processes by the Langmuir–Hinshelwood mechanism, whereas the interaction of
molecules with surface active centers (e 0 ) can initiate surface chemical processes by
the Eley–Rideal mechanism. Finally, the exchange of free charge carriers and
excitons between the bulk and the surface can occur by diffusion or drift (e).
Fundamentals 21
In the Eley–Rideal mechanism, proposed in 1938 by D. D. Eley and E. K.
Rideal, only one of the reactant molecules adsorbs and the other reacts with it
directly from the gas phase, without adsorbing:
Ag þ Ss ÐASads ð1:31Þ
ASads þ Bg ! Product ð1:32Þ
The Langmuir–Hinshelwood mechanism proposes that both molecules adsorb

and then undergo a bimolecular reaction:
Ag þ Ss ÐASads ð1:33Þ
Bg þ Ss ÐBSads ð1:34Þ
ASads: þ BSads: ÐProduct ð1:35Þ

Figure 1.17 shows the two mechanisms.
The Langmuir–Hinshelwood model (LH) is widely applied to liquid- and gas-
phase systems (with minor variations) for the degradation of organic substrates
on TiO2 surfaces in the presence of oxygen.40–46 This model successfully explains
the kinetics of reactions that occur between two adsorbed species – a free radical
and an adsorbed substrate, or a surface-bound radical and a free substrate. The
Eley-Rideal mechanism
Ag
Bg
Product
SSS AS
ASads
ads
A molecule adsorbs Another molecule interacts A product is formed

onto the surface with the adsorbed one and desorbs
Langmuir-Hinshelwood mechanism
Ag Bg
BSads Product
SSS SSS
ASads
Two molecules adsorb They diffuse on the surface A product is formed

onto the surface and interact with each other and desorbs
Figure 1.17 Graphic models of the Eley–Rideal and Langmuir–Hinshelwood

mechanisms.
22 Chapter 1
main assumptions of the LH model are (i) the adsorption equilibrium is
established at all times and the reaction rate is less than the rate of adsorption or
desorption; (ii) the reaction is assumed to occur between adsorbed species whose
coverage on the catalyst surface is always in equilibrium with the concentration
of the species in the fluid phase, so that the rate-determining step of the pho-
tocatalytic process is the surface reaction. The concentrations of adsorbed
species are determined by adsorption equilibrium by means of a suitable iso-
therm. Notably, the simple rate form of the LH approach may have origins that
take into account different photoreaction mechanisms.47–49
The decrease of the amount of a species in a batch photocatalytic system
working in a liquid–solid regime is the combined result of photoadsorption and
photoconversion processes. To describe this behavior, a molar balance applied
to the species at any time43 can be written as:
nT ¼ nL þ nS ð1:36Þ
where nT is the total number of moles present in the photoreactor, nL the

number of moles in the fluid phase and nS the number of moles photoadsorbed
on the solid. By dividing Equation (1.36) by the volume of the liquid phase, V,
the following relation is obtained:
nS
CT ¼ CL þ ð1:37Þ
V
where CT is the total concentration of the species and CL the concentration in

the liquid phase.
Both substrate and oxygen must be present in the system for the occurrence of
the photoreaction; then it is assumed that the total disappearance rate of substrate
per unit surface area, rT, follows second-order kinetics (first order with respect to
the substrate coverage and first order with respect to the oxygen coverage):
1 dnT
rT ¼ k 0 0 ySub yOx ð1:38Þ
S dt
where S is the catalyst surface area, t the time, k00 the second order rate constant
and ySub and yOx are the substrate and oxygen fractional coverage of the surface,
respectively; ySub and yOx are defined as follows:
nS
ySub ð1:39Þ
WNS
nS;Ox
yOx ð1:40Þ
WNS;Ox
where nS,Ox is the number of moles of oxygen photoadsorbed on the solid, N*S and
N*S,Ox are the maximum capacity of photoadsorbed moles of substrate and oxy-
gen, respectively, on the unit mass of irradiated solid and W is the mass of catalyst.
Fundamentals 23
By considering oxygen that is continuously bubbled into the dispersion,
during the experimental runs, its concentration in the liquid phase does not
change and it is always in excess. Then the yOx term of Equation (1.38) does not
depend on time, i.e., it is constant. By defining k ¼ k00 yOx, Equation (1.38) turns
a pseudo-first order rate equation:
1 dnT
rT ¼ kySub ð1:41Þ
S dt
where k is the pseudo-first order rate constant. Introducing the liquid volume,
V, and the surface area per unit mass of catalyst, SS, in Equation (1.41), the
following relation is obtained:
1 dnT 1 dCT
rT ¼ V ¼ kySub ð1:42Þ
S dt SS W dt
The kinetic information on a photoprocess consists of knowledge of sub-

strate concentration values in the liquid phase, CL, as a function of irradiation
time. Then the CT and the ySub variables of Equation (1.42) must be trans-
formed as a function of CL. For this reason it is necessary to choose a suitable
adsorption isotherm for ySub, i.e., a relationship between ySub [and therefore nS,
see Equation (1.39)] and CL, while Equation (1.37) coupled with the chosen
isotherm may be used for CT. Therefore, Equation (1.42) may be formally
written in the following way:
1 d
V CT ðCL Þ ¼ kySub ðCL Þ ð1:43Þ
SS W dt
For a batch photocatalytic runs, by hypothesizing that the main assumptions

of the LH model are valid, the substrate concentration values measured in the
liquid phase at a certain time represent the substrate concentration in equili-
brium with an (unknown) substrate amount photoadsorbed on the catalyst
surface. This feature belongs to all the measured values of substrate con-
centration except for the initial one. The substrate concentration measured at the
start of a photoreactivity run is characteristic of a system without irradiation.
Then, during the fitting of a kinetic model to the experimental data, regression
analysis must be performed by using the values of concentration measured
throughout the run, excluding the initial substrate concentration under dark.50
1.2.1 Langmuir Isotherm

The Langmuir isotherm theory51 assumes that the substrate is adsorbed in a
monolayer over a homogenous adsorbent surface. A plateau characterizes the
Langmuir isotherm; therefore, a saturation point is reached where no further
24 Chapter 1
adsorption occurs. Adsorption is assumed to take place at specific homo-
geneous sites within the adsorbent. Once a molecule occupies a site, no further
adsorption can take place at that site. The Langmuir model assumes that the
catalyst surface is completely uniform, i.e., (i) the adsorption onto the surface
of each molecule has equal activation energy and (ii) no transmigration of
adsorbate in the plane of the surface occurs. These assumptions are hypothe-
sized here to describe photoadsorption. The Langmuir adsorption isotherm is
described by the following relationship:
nS KL CL
ySub ¼ ð1:44Þ
WNS 1 þ KL CL
where K*L is the photoadsorption equilibrium constant, related to the free

energy of photoadsorption, and N*S the monolayer adsorption capacity. K*L may
be considered a measure of the intrinsic photoreactivity of the catalyst surface.
By solving Equation (1.44) with respect to nS and substituting in Equation
(1.37) we obtain:
WNS KL CL
V 1 þ KL CL
Substituting in Equation (1.42) the Langmuir relationship [Equation (1.44)]

gives the following relation:
V dCT KL CL
¼k ð1:46Þ
WSS dt 1 þ KL CL
Taking the derivative of Equation (1.45) with respect to time yields:

" #
dCT WNS KL 1 dCL
¼ 1þ 2 ð1:47Þ
dt V
1 þ K CL dt
L
Substituting Equation (1.47) into the left-hand term of Equation (1.46), one
obtains:
" #
V WNS KL 1 dCL KL CL
1þ ¼ k ð1:48Þ
WSS V 1 þ K CL
2 dt 1 þ KL CL
L
and, upon rearranging and separating the variables, the following differential
equation is obtained:
V 1 dCL V 1 1 NS dCL

dCL ¼ dt ð1:49Þ
WSS kKL CL WSS k SS k CL 1 þ KL CL
Equation (1.49) gives the evolution of concentration in the liquid phase with
the irradiation time of a species in photoadsorption equilibrium on the catalyst
surface, over which the species undergoes a slow transformation process. On
Fundamentals 25
this basis, the integration of Equation (1.49) must be performed with the lim-
iting condition that at t ¼ 0 the substrate concentration in the liquid phase is
that in equilibrium with the initial photoadsorbed amount, CL,0; this initial
concentration is unknown but it may be determined by regression analysis
carried out with the experimental data obtained after the start of irradiation.
The integration yields:

V 1 CL;0 V 1 1 NS 1 þ KL CL CL;0
ln þ ðCL;0 CL Þ þ ln ¼t ð1:50Þ
WSS kKL CL WSS k SS k 1 þ KL CL;0 CL
Equation (1.50) contains four unknown parameters, K*L, N*S, k and CL,0,
which may be determined by a best fitting procedure.
1.2.2 Freundlich Isotherm

The Langmuir theory of adsorption is an approximation of real surfaces. If the
Langmuir theory was universally valid, we should expect the heat of adsorption
to remain constant with increasing values of the coverage y. In some cases the
heat of adsorption decreases with coverage. One explanation is that the surfaces
of the catalysts and of the solids are energetically heterogeneous. An assump-
tion generally used in describing the physical chemistry of real adsorbed layers
is that the surface sites are different, the so-called biographical non-
uniformity.44 By applying the Langmuir adsorption isotherm to a distribution
of energies among the sites such that the heat of adsorption decreases loga-
rithmically with coverage, the Freundlich isotherm is derived;51 it is described
by the following relationship:
nS 1=n
ySub ¼ KF CL ð1:51Þ
WNS
where K*F is the Freundlich isotherm constant, which indicates the relative
adsorption capacity of the adsorbent, and n is a dimensionless parameter
indicative of the intensity of the adsorption. The parameter n represents the
mutual interaction of adsorbed species; a value of n greater than unity indicates
the occurrence of repulsion among adsorbed molecules. The Freundlich rela-
tion is an exponential equation that assumes that the concentration of adsor-
bate on the adsorbent surface increases by increasing the adsorbate
concentration in the liquid phase. By using the empirical form of the Freundlich
isotherm, there is no limit to adsorption; this is not in agreement with the
chemisorption theory. Statistical derivation of this isotherm, however, sets a
value of the Freundlich maximum adsorption capacity. Solving Equation (1.51)
with respect to nS and substituting in Equation (1.37), gives:
WNS 1=n
CT ¼ CL þ KF CL ð1:52Þ
V
26 Chapter 1
Substituting the Freundlich relationship [Equation (1.51)] in Equation (1.42)
affords the following relation:
V dCT 1=n
¼ kKF CL ð1:53Þ
WSS dt
The derivative of Equation (1.52) with respect to time yields:

dCT WNS KF 1 1n dCL
¼ 1þ C n
ð1:54Þ
dt V n L dt
obtains:

V WNS KF 1 1n dCL 1=n
1þ CLn ¼ kKF CL ð1:55Þ
WSS V n dt
and by rearranging and separating the variables the following differential equa-
tion is obtained:
V 1 dCL 1 NS dCL

¼ dt ð1:56Þ
WSS kKF C 1=n SS kn CL
L
As with Langmuir adsorption isotherm, Equation (1.56) is integrated with the

condition that at t ¼ 0 the substrate concentration in the liquid phase is that in
equilibrium with the initial photoadsorbed amount, CL,0; this initial concentration
is unknown but it may be determined by regression analysis carried out with the
experimental data obtained after the start of irradiation. The integration yields:
V 1 n ðn1Þ=n ðn1Þ=nÞ
1 N C
S L;0
CL;0 CL þ ln ¼t ð1:57Þ
WSS kKF n 1 SS kn CL
Equation (1.57) contains five unknown parameters, K F*, N S*, n, k, and CL,0, which
may be determined by a best fitting procedure.
1.2.3 Redlich–Peterson Isotherm

The Redlich–Peterson (R-P) isotherm52 model combines elements from both the
Langmuir and Freundlich equation, and the mechanism of adsorption is a
hybrid one and it does not follow ideal monolayer adsorption. The R-P isotherm
is an empirical equation, designated the ‘‘three parameter equation,’’ that may
be used to represent adsorption equilibria over a wide concentration range.53–56
The R-P adsorption isotherm is described by the following relationship:
nS KR -P CL
¼ ð1:58Þ
W 1 þ aR-P CLb
Fundamentals 27
where K*R-Pand a*R-Pare R-P isotherm constants that refer to the adsorption
capacity and the surface energy, respectively. The exponent b is the hetero-
geneity factor, which lies between 1 and 0. The equation can be reduced to the
Langmuir equation as b approaches 1 while it becomes the Henry’s law equation
when b ¼ 0. By solving Equation (1.58) with respect to nS and substituting in
Equation (1.37), the result is:
W KR -P CL
V 1 þ aR-P CLb
In the cases of Langmuir and Freundlich isotherms it has been assumed that the
total disappearance rate of substrate per unit surface area, rT, follows a pseudo-
first order kinetics with respect to the substrate concentration, which is
expressed by its fractional coverage. The same assumption is made for R-P
isotherm; however, as the R-P isotherm relates an adsorbed amount (and not a
fractional coverage) with the equilibrium concentration in the liquid phase, the
rT term is written as:
V dCT nS
rT ¼ kCSurface ¼ k ð1:60Þ
WSS dt WSS
where CSurface is the surface concentration of adsorbed species (adsorbed moles/

catalyst surface area).48 Substituting in Equation (1.60) the R-P relationship
[Equation (1.58)] produces:
V dCT KR -P CL
¼k ð1:61Þ
W dt 1 þ aR-P CLb
Taking the derivative of Equation (1.59) with respect to time yields:

2 3

dCT 6 WKR -P 1þ aR-P CLb 1 bKR -P 7 dCL
¼ 41 þ 2 5 ð1:62Þ
dt V dt
1þ aR-P CLb
obtains:
2 3

V6 WKR -P 1þ aR-P CLb 1 bKR -P 7 dCL KR-P CL
41 þ 2 5 ¼k ð1:63Þ
W V
1þ aR-P CLb
dt 1 þ aR-P CLb
and, upon rearranging and separating the variables, the following differential
equation is obtained:
28 Chapter 1
V dCL aR-P V 1 dCL
CLb1 dCL þ
WkKR-P CL WkKR -P k CL 1 þ a C b
R- P L
ð1:64Þ
VaR-P 1 bKR -P CLb1 dCL
¼ dt
WkKR -P 1 þ aR-P CLb
As with previous adsorption isotherms, Equation (1.64) is integrated with the

condition that at t ¼ 0 the substrate concentration in the liquid phase is that in
equilibrium with the initial photoadsorbed amount, CL,0; again, this initial
concentration is unknown but it may be determined by regression analysis
carried out with the experimental data obtained after the start of irradiation.
The integration yields:
!
V CL0 aR-P V b b
1 b
1 þ aR-P CLb CL0
ln þ CL0 CL þ ln
WkKR -P CL WkbKR -P kb b
1 þ aR-P CL0 CLb
!
b
V 1 bKR -P 1 þ aR-P CL0
þ ln ¼t
WkbKR -P 1 þ aR-P CLb
ð1:65Þ
Equation (1.65) contains five unknown parameters, K*R-P, a*R-P, b, k and CL0,
which may be determined by a best fitting procedure.
1.2.4 Light Intensity Dependence

In most kinetics studies of a photocatalytic reaction, the observed variation of the
initial degradation rate of an organic substrate ( r) with its initial concentration
is generally well described by a Langmuir–Hinshelwood type kinetic equation:
KL CL
ðrÞ ¼ k ð1:66Þ
1 þ KL CL
Initially, only k was considered to be dependent on the incident light,26,57–60

which is directly related to the absorbed photons; however, K*L is usually
greater than the Langmuir adsorption constant under dark conditions and now
it is accepted that this parameter is also light intensity dependent.61–66
In the following, the different mechanisms proposed for this light-intensity
dependence are shown.
Emeline et al. have proposed Eley–Rideal and Langmuir–Hinshelwood
based mechanisms:62–65,67
kER ¼ a I ð1:67Þ
b
KER ¼ I ð1:68Þ
d
Fundamentals 29
and:
aI
kLH ¼ ð1:69Þ
eþd I
ðe þ d I ÞKads
KLH ¼ ð1:70Þ
dI
where I is the incident light intensity, Kads is the dark Langmuir adsorption
constant, a, b, d and e are constants; a plot of 1/KLH versus kLH yields a straight
line passing from the origin of the axis. This insight was confirmed for the
photodegradation of phenol but studies with 4-chlorophenol showed a straight
line with a positive intercept.
Ollis61 has explained this behavior by considering that the adsorption/des-
orption kinetics of the key substrate, A, are influenced by the oxidation process
under pseudo-steady state conditions:
k1
Aliquid !
Aads ð1:71Þ
k1
kLH
Aads ! products ð1:72Þ
Step (1.72) involves oxidation of the organic species by a photogenerated

surface hydroxyl radical, which depends upon the incident light intensity. Then:
kLH ¼ a I b ð1:73Þ
where a is a proportionality constant and b is a constant whose value is usually

equal to 1 and 0.5 under low and high intensity irradiation, respectively. A
square-root dependence can be found for high light intensity due to the pre-
dominance of electron–hole recombination.
The pseudo-steady state reaction proposed by Ollis61 involves a kinetic
expression in which kLH is given by Equation (1.73) and:
k1
KLH ¼ ð1:74Þ
k1 þ a I b
This simple model predicts not only the light intensity dependence for kLH and
KLH but also the straight line (of gradient 1/k1) in the plot of 1/KLH versus kLH
with a positive intercept in the case of 4-chlorophenol degradation and a zero
intercept for phenol photodegradation, as previously described.
It is well known that the reaction rate depends in a complex way on the light
intensity; moreover, the reactor geometry influences strongly the ratio between
backward reflected and incident photon flow. The apparent napierian extinc-
tion coefficient for slurries, which is a parameter related to the absorption
photon flow, decreases as the particle size increases.68
30 Chapter 1
Evaluation of the local volumetric rate of photon absorption as well as the
determination of scattering and absorption coefficient have been studied.69 In a
solid–liquid system, photon absorption by the photocatalyst is strictly related
to scattering, which makes the kinetics analysis more difficult.
The rate of backward reflected photon flow can be determined by an
extrapolation method68,70–73 that consists in measuring the rate of transmitted
photon flow as a function of the suspension volume, V:
FT ¼ F 0 expðE CCat V Þ ð1:75Þ
where F 0 is the rate of photons able to penetrate the suspension, E is the

apparent Napierian extinction coefficient of the suspension and CCat the cat-
alyst concentration.
Application of a macroscopic photon balance on the photoreactor at the
limit condition of V ¼ 0 allows determination of the backward reflected photon
flow Fr:
Fr ¼ Fi F 0 ð1:76Þ
The absorbed photon flow Fa can be obtained by the following photon

balance on the system:
Fa ¼ Fi FT Fr ð1:77Þ
Nevertheless, when the mean particle size is of the same order of magnitude
as the wavelength used, inelastic scattering phenomena can occur and this
procedure cannot be used.
In photocatalytic reactions, the photons absorbed by the photocatalyst may
be considered as a reactant species. Therefore, the spatial distribution of their
absorption rate is an important issue in order to interpret experimental results,
to develop kinetic models and to optimize or to scale-up a photocatalytic
reactor. The Monte Carlo approach can be employed to obtain values of the
local volumetric rate of photon absorption (LVRPA or ea,v).
In general terms, the Monte Carlo method applied to the radiation field
resolution consists of tracking the trajectory of a great number of photons. In
doing so, the basic laws of geometric optics are applied (such as Snell refraction
law and Fresnel reflectivity equation), as well as the ray tracing technique. The
LVRPA can be constructed out of the series of events that is likely to occur for
each of the photons that take part in the simulated experiment. The Monte
Carlo method has been employed successfully in the analysis and modeling of
photocatalytic reactors.74–80
1.3 Radiation Sources

The performance of a photoreactor depends strongly on the irradiation source.
Six main types of radiation sources may be used: (1) arc lamps, (2) fluorescent
Fundamentals 31
lamps, (3) incandescent lamps, (4) lasers, (5) light-emitting diodes (LEDs) and
(6) solar radiation.
1.3.1 Arc Lamps

In arc lamps the emission is obtained by activation of a gas by collision with
accelerated electrons generated by an electric discharge between two electrodes,
typically made of tungsten. The type of lamp is often named according to the
gas contained in the bulb, including neon, argon, xenon, krypton, sodium,
metal halide and mercury. In particular for mercury lamps, the following
classification, based on the Hg pressure, has been made:
1. Low pressure: the lamp contains Hg vapor at a pressure of ca. 0.1 Pa at

298 K and it emits mainly at 253.7 and 184.9 nm.
2. Medium pressure: this lamp contains Hg vapor at a pressure from 100 to
several hundred kPa. It emits mostly from 310 to 1000 nm with most
intense lines at 313, 366, 436, 576 and 578 nm.
3. High pressure: this lamp contains Hg vapor at a pressure equal or higher
than 10 MPa and it emits a continuous background between ca. 200 and
1000 nm with broad lines.
4. Hg-Xe. This lamp is used to simulate solar radiation as it is an intense
ultraviolet, visible and near-IR radiation source. The lamp contains a
mixture of Hg and Xe vapors at different concentrations under high
pressure. The presence of Hg vapor increases emission in the UV region.
The above lamps are usually cylindrical, with the arc length increasing as the
pressure decreases and power increases. The power ranges from a few watts to
ca. 60 000 W. Generally, medium- and high-pressure mercury lamps need to be
cooled by circulating liquids.
1.3.2 Fluorescent Lamps

Fluorescent lamps are filled with gas containing a mixture of low-pressure
mercury vapor and argon (or xenon), more rarely argon–neon, sometimes even
krypton. The inner surface of the lamp is coated with a fluorescent (often
slightly phosphorescent) coating made of varying blends of metallic and rare-
earth phosphor salts. The cathode is generally made of coiled tungsten coated
with a mixture of strontium, barium and calcium oxides that have a relatively
low thermo-ionic emission temperature. When the light is turned on, the
cathode is heated sufficiently to emit electrons. These electrons collide with gas
atoms, which are ionized to form a plasma by a process of impact ionization.
As a result the conductivity of the ionized gas rises, allowing higher currents to
flow through the lamp. The mercury, which exists at a stable vapor pressure
equilibrium point of about one part per thousand inside the tube (with the
noble gas pressure typically being about 0.3% of standard atmospheric
32 Chapter 1
pressure), is then likewise ionized, causing it to emit light in the ultraviolet
(UV) region of the spectrum, predominantly at wavelengths of 253.7 and
185 nm. Fluorescent lighting is efficient because low-pressure mercury
discharges emit about 65% of their total light at the 254 nm line (also about
10–20% of the light emitted in UV is at the 185 nm line). The UV light is
absorbed by the bulb’s fluorescent coating, which re-radiates the energy at
lower frequencies (longer wavelengths: two intense lines of 440 nm and 546 nm
wavelengths appear on commercial fluorescent tubes) to emit visible light. The
blend of phosphors controls the color of the light and, along with the bulb’s
glass, prevents escape of the harmful UV light. Actinic fluorescent tubes have
an emission in the near-UV region (ca. 360 nm) due to their particular fluor-
escent coating.
1.3.3 Incandescent Lamps

The emission of incandescent lamps is obtained by heating at very high tem-
perature suitable filaments of various substances by current circulation.
One of the most used incandescent lamps is the halogen lamp, wherein a
tungsten filament is sealed into a small envelope filled with a halogen gas
such as iodine or bromine. A tungsten-halogen lamp creates an equilibrium
reaction in which the tungsten that evaporates when giving off light is pre-
ferentially re-deposited at the hot-spots, thereby preventing the early failure of
the lamp. This also allows halogen lamps to be run at higher temperatures that
would cause unacceptably short lamp lifetimes in ordinary incandescent lamps,
allowing for higher luminous efficacy, apparent brightness and whiter color
temperature. Because the lamp must be very hot to create this reaction, the
envelope of the halogen lamp must be made of hard glass or fused quartz,
instead of ordinary soft glass which would soften and flow too much at such
temperatures.
In applications that require ultraviolet radiation, the lamp envelope is made
out of undoped quartz. Thus, the lamp becomes a source of UV-B radiation. A
typical halogen lamp is designed to run for about 2000 h, which is twice as long
as a typical incandescent lamp.
1.3.4 Lasers
A laser (light amplification by stimulated emission of radiation) is a device
that emits light through a specific mechanism. This is a combined quantum-
mechanical and thermodynamic process. A typical laser emits light in a narrow
and well-defined beam and with a well-defined wavelength (or color). This is in
contrast to a light source such as the incandescent light bulb, which
emits in almost all directions and over a wide spectrum of wavelengths. All
these properties are summarized in the term coherence. A laser consists of a
gain medium inside an optical cavity, to supply energy to the gain medium.
The gain medium is a material (gas, liquid or solid) with appropriate optical
Fundamentals 33
properties. In its simplest form, a cavity consists of two mirrors arranged
such that light bounces back and forth, each time passing through the gain
medium. Typically, one of the two mirrors, the output coupler, is partially
transparent. All light that is emitted by the laser passes through this output
coupler.
Light of a specific wavelength that passes through the gain medium is
amplified (increases in intensity); the surrounding mirrors ensure that most of
the light makes many passes through the gain medium. Part of the light that is
between the mirrors (i.e., in the cavity) passes through the partially transparent
mirror and appears as a beam of light. The process of supplying the energy
required for the amplification is called pumping and the energy is typically
supplied as an electrical current or as light at a different wavelength. In the
latter case, the light source can be a flash lamp or another laser. Most practical
lasers contain additional elements that affect properties such as the wavelength
of the emitted light and the shape of the beam.
1.3.5 Light Emitting Diodes (LEDs)

LEDs are special p-n junction diodes formed by a thin layer of doped semi-
conductor material. They are based on semiconductor optical properties to
produce photons by the recombination of electron–hole pairs. Electrons and
holes are injected in a recombination zone through two parts of the diode
doped in different ways, ‘‘n’’ type impurities for electrons and ‘‘p’’ type for
holes. Figure 1.18 shows a working scheme. Ultraviolet light is achievable by
using GaN as the active layer, with emission in the near-UV region with
wavelengths around 350–370 nm. In addition, nitrides containing aluminium,
such as AlGaN and AlGaInN, can be used to achieve shorter wavelengths,
whereas the use of aluminium nitride enables wavelengths down to 210 nm to
be obtained. Figure 1.19 shows the main parts of a LED.
light emission
hole electron
p-type n-type
+ -
EC
EC
E (eV) EF
EF
EV
EV
Figure 1.18 Working scheme and energetic levels in a LED.

34 Chapter 1
Epoxy lens-case
Wire bond
Reflective cavity
Semiconductor die
Lead frame
Flat spot
+ -
Anode Catode
Figure 1.19 Main parts of a LED.
1.8 1000
Irradiance per wavelength [W·m-2·nm-1]
1.6 900
800
1.4 Integrated irradiance [W·m-2]
700
1.2
600
1.0
500
0.8
400
0.6
300
0.4 200
0.2 100
0 0
300 400 500 600 700 800 900 1000
Wavelength [nm]
Figure 1.20 ASTM global irradiance standard solar spectrum (AM 1.5) up to a
wavelength of 1000 nm, incident on a plane tilted 381 facing south,
normalized to 1000 W m2 for the whole spectrum.
1.3.6 Solar Resources

The earth receives about 1.7 1014 kW of solar radiation (1.5 1018 kWh per
year). Extraterrestrial radiation has an intensity of 1367 W m2 in the wave-
length range 200–5000 nm, which is reduced to 280–4000 nm when it reaches
the ground, due to absorption phenomena by atmospheric compounds such as
ozone, oxygen, carbon dioxide and water vapor as well as aerosols, clouds, etc.
Fundamentals 35
The solar radiation that reaches the planet without being absorbed or scat-
tered is called direct beam radiation, whereas radiation that reaches the ground
but has been dispersed beforehand is called diffuse radiation; the sum of both is
called global radiation. Figure 1.20 shows the standard solar spectrum at sea
level, where the spectral irradiance data are for the sun at a solar zenith angle of
48.191. This zenith angle corresponds to an air mass (AM) of 1.5, which is the
ratio of the direct-beam solar irradiance path length through the atmosphere at
a solar zenith angle of 48.191 to the path length when the sun is in the zenith.
The radiation effectively reaching ground level changes strongly due to
several factors, such as date, time, geographic latitude, atmospheric conditions
(aerosols, humidity, etc.) or cloudiness. To judge the feasibility and profitability
of solar applications at a specific site, studies have to be performed to estimate
or to measure the amount of radiation actually available at the specific site
throughout the year.
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CHAPTER 2
Powders versus Thin Film

Preparation
2.1 Introduction
Numerous papers have been published in last decade on the preparation,
characterization and use in photocatalytic studies of the most common TiO2
polymorphs, i.e., anatase and rutile phases, both as powdered forms or films
onto various types of supports, mainly glasses. Few studies have been con-
cerned with the brookite phase, due to the difficulty in obtaining it straight-
forwardly in the absence of the other phases. Little information is available on
the other rarer phases, reported below in Table 2.1, and they generally are not
used to carry out heterogeneous photocatalytic reactions.
Important manufacturing processes applied to prepare TiO2 powders, which
are used mainly as base pigments in the anatase or rutile phase, are the sulfate,
chloride and flame pyrolysis processes.
The sol-gel, hydrothermal, solvothermal, sol, laser pyrolysis and microwave
methods reported in the literature are generally more suitable for scientific
purposes.1
The main techniques used to prepare, instead, photocatalytic films are dip-
coating, spin-coating, flow coating, (plasma) spray drying and spray-pyrolysis
methods, physical vapor deposition (PVD), chemical vapor deposition (CVD),
chemical bath deposition, thermal or anodic oxidation, and electrophoretic
deposition.
Any explanation of the photoactivity of TiO2 powders must carefully con-
sider not only the type of phase(s) present and its (their) intrinsic electronic
properties but also its (their) morphological, structural and surface physico-
chemical properties. Surface hydroxylation, crystallinity, size of particles and
porosity are of paramount importance among the parameters to be evaluated.
Note, for instance, the light absorption blue-shift (quantum size effect)
observed for TiO2 nanoparticles and the influence of particle size in the ana-
tase-rutile transition temperature.

41
42 Chapter 2
Table 2.1 Natural and synthetic TiO2 forms.
Polymorphic form Crystal system Synthesis
Rutile Tetragonal
Anatase Tetragonal
Brookite Orthorhombic
TiO2(II)-(a-PbO2-like form) Orthorhombic
TiO2(OI) Orthorhombic
Baddeleyite-like form Monoclinic
(seven-coordinate Ti)
Cubic form Cubic
TiO2(OII), cotunnite; (PbCl2)-like Orthorhombic
TiO2(B) Monoclinic Hydrolysis of K2Ti4O9
followed by heating
TiO2(H), hollandite-like form Tetragonal Oxidation of the related
potassium titanate
bronze, K0.25TiO2
TiO2(R), ramsdellite-like form Orthorhombic Oxidation of the related
lithium titanate bronze
Li0.5TiO2
The same considerations apply to films, and in addition it is essential to

consider their thickness, transparency and roughness. Transparency, for
instance, is an essential property for superhydrophilic mirrors or glasses
that give rise to an antifouling effect without formation of steam on their
surface. The superhydrophilicity of a TiO2 film, which usually increases
under irradiation, can be verified by measuring the so-called contact angle of a
drop of water onto its surface. The higher the angle, the higher is the
hydrophilicity.
The existing scientific literature does not satisfactorily highlight the differ-
ences between powders and films as far as their scientific and practical utili-
zations are concerned.
Notably, the surface area of the photoactive films is smaller than that
of the powders and consequently the photodegradation rate of organic pollu-
tants is generally lower than that observed in the presence of powders. Despite
this, to-date practical applications of films are more numerous, as it can be
noticed by reading other chapters of this book. The main reason for this is that
it is not necessary to separate the photocatalyst from the reaction ambient in
liquid–solid systems and films of TiO2 on various supports can be used to
successfully reduce the indoor pollution, while also killing some kinds of bac-
teria, if present.
This chapter is confined to the main preparation methods of pure poly-
crystalline or nanostructured anatase, rutile and brookite TiO2 polymorphs
mainly used in photocatalytic studies and to the most popular techniques
employed to prepare TiO2 films. Only a few examples, with essential infor-
mation from the literature, are given; interested readers are invited to scrutinize
the cited papers for more details.
Powders versus Thin Film Preparation 43
2.2 Structures and some Properties of the various TiO2
Polymorphs
TiO2 occurs in nature as rutile, anatase and brookite minerals. Rutile is the
most abundant TiO2 polymorph, is an important minor constituent in
natural rocks and is isostructural with stishovite. For general nanostructured
samples, the transformation sequence between anatase and brookite depends
on the initial particle sizes since particle size determines the thermodynamic
phase stability.2,3 All the allotropic phases contain six-coordinated titanium
atoms.
Rutile is the most stable phase for particle size above 35 nm, anatase for
particle size below ca. 11 nm, whereas brookite has been found to be the most
stable phase for nanoparticles in the 11–35 nm range. Figure 2.1 shows sche-
matic structures and photographs of the main TiO2 phases.
In addition to rutile, anatase and brookite there are five high-pressure forms:
a-PbO2-like form, TiO2(OI), baddeleyite-like form, cubic form, and TiO2(OII)
cotunnite-like form.4,5 Moreover, three forms are produced synthetically, i.e.,
monoclinic TiO2(B),6 tetragonal TiO2(H) hollandite-like form7 and TiO2(R)
ramsdellite-like orthorhombic form.8 As far as the high-pressure forms are
concerned, the a-PbO2-like is a dense post-rutile TiO2 phase with Raman bands
identical to those of the a-PbO2-structured polymorph of TiO2 synthesized in a
dynamic laboratory experiment (2% denser than rutile). The baddeleyite-like is
an ultradense post-rutile polymorph of TiO2 (11% denser than rutile) with
monoclinic a lattice, isostructural with the baddeleyite ZrO2 polymorph, and
the titanium cation is coordinated with seven oxygen anions. The cotunnite-like
polymorph is a cotunnite-structured titanium oxide that represents the hardest
oxide known. This is a new polymorph of TiO2, where titanium is nine-coor-
dinated to oxygen in the cotunnite (PbCl2) structure.9 Table 2.1 summarizes the
above-cited polymorphic forms.
TiO2 is used in a wide range of applications in ceramics and in electric devices
and moreover as a gas sensor, a white pigment (e.g., in paints and cosmetic
products), a corrosion-protective coating and an optical coating. It plays an
important role in earth sciences, in biocompatibility of bone implants, is spacer
materials, and finds applications in nanostructured form in Li-based batteries
and electrochromic devices. TiO2 is also used in heterogeneous photocatalysis
both in powdered form and as film on various types of supports and in solar
cells for the production of hydrogen and electric energy.10
2.3 Preparation Methods of Powdered TiO2

Many methods have been used to prepare powdered TiO2, mainly in the ana-
tase or in the rutile phase. In the following, after a short presentation of some
industrial processes, the preparations more frequently found in the scientific
literature will be presented. They will be examined in terms of the photo-
catalytic applications of TiO2 by describing also briefly some papers reporting
44 Chapter 2
Anatase Rutile Brookite
[001]
[101]
Anatase
[001]
Ti O
c
[101]
a
a
[100]
Rutile
Brookite
Figure 2.1 Structures and photographs of crystals of the main polymorphs of TiO2.
(Photograph courtesy of http://www.probertencyclopaedia.com.)
the formation under particular experimental conditions of nanorods, nano-
tubes and nanowires.
2.3.1 Sulfate Process

The sulfate process was the first commercial process for manufacturing pow-
dered TiO2. The first used starting raw material was ilmenite (FeTiO3), but
subsequently other ores with a much higher TiO2 content have been chosen.
The ore is subjected to drying and grinding and then it is reacted with
concentrated sulfuric acid (exothermic digestion reaction). The experimental
conditions are controlled (minimum amount of acid should be used) to
maximize the conversion of TiO2 into water-soluble titanyl sulfate. The resul-
tant dry, green-brown cake of metal sulfates is dissolved in a weak acidic
aqueous solution, the temperature is lowered to avoid premature hydrolysis,
and the solution clarified by settling and chemical flocculation. The resultant
clear solution is then further cooled to crystallize the by-product FeSO4 7H2O,
which is separated.
The insoluble mud so-obtained is washed to recover the titanyl sulfate liquor,
which is filtered to remove the insoluble impurities. The solution is evaporated
to a precise composition and hydrolyzed to obtain a pulp consisting mainly of
clusters of colloidal hydrous titanium oxide. Precipitation is induced by a
seeding or nucleation technique. The pulp is then separated from the mother
liquor and washed to remove residual traces of metallic impurities, using
sometimes chelating agents. The washed pulp is treated with chemicals that
adjust the physical texture and act as catalysts in the calcination step. This
process can produce either anatase or rutile crystal forms depending on the
additives used before the calcination process.
2.3.2 Chloride Process

The starting material for the chloride process is generally a mineral rutile
containing over 90% TiO2. An ore blend mixed with a source of carbon is
reacted in a fluidized bed with chlorine at ca. 1173 K. The exothermic reaction,
which needs accurate temperature control, yields TiCl4 together with the
chlorides of all the impurities present. The mixed chlorides are cooled and the
low-volatile chloride impurities (e.g., manganese, chromium and iron) are
separated by condensation and removed from the gas stream along with any
unreacted solid starting materials. After condensation of the TiCl4 vapor, an
extremely pure, colorless, mobile liquid TiCl4 intermediate product, freezing at
249 K and boiling at 409 K, is produced by fractional distillation. The success
of the chloride process is due to this stable intermediate, which can be purified,
tested, stored, reprocessed and handled as a liquid or vapor. Moreover,
potentially discoloring trace contaminants can be eliminated with benefit to
pigment color because the distillation process is a vapor-phase process. The
second stage in the chloride process is the oxidation of TiCl4 to TiO2. TiCl4 is
46 Chapter 2
reacted with O2 (exothermic reaction) to form TiO2 with liberation of chlorine,
which is recycled to the chlorination stage. Owing to the high temperature, only
rutile phase is produced. After cooling, the gas stream passes through a
separator to collect the TiO2 particles and it is treated to remove adsorbed
chlorine.
Notably, in both sulfate and chloride processes the commercial TiO2, usually
sold as a pigment, is subjected to a surface treatment with a combination of
Al2O3, SiO2 and/or ZrO2. Sometimes, organic species are also used, such as for
instance polyols, which are alcohols containing multiple hydroxyl groups. The
aim of the treatment is to improve the wetting, stability of the dispersion in
different media, compatibility with the binder, color stability, and durability.
It is imperative to know the nature and the extent of additives and impurities
when commercial powdered TiO2 samples are used as photocatalysts, as their
presence could significantly influence the photoactivity.
2.3.3 Flame Pyrolysis Process

This process has been used to prepare the most popular commercial sample
used in photocatalytic studies, i.e., Degussa P25, but some research papers11–13
also report its use to prepare TiO2 soft agglomerates (or just agglomerates) and
hard agglomerates (aggregates).
In ref. 13, for instance, titanium tetraisopropoxide, used as the precursor,
diluted (0.8 M) with xylene, was injected (5 ml min1) by a syringe pump into the
reactor through the center capillary of the flame synthesis pyrolysis nozzle.
Oxygen (5 ml min1) was fed through the surrounding annulus, dispersing
the solution into droplets. The pressure drop at the nozzle was held constant at
1.5 bar by adjusting the annulus gap width. A supporting premixed CH4/O2
(ratio: 1.5/3.2) flame surrounding the dispersion oxygen annulus ignited and
stabilized the spray flame. The extent of agglomeration or aggregation was a
function of the applied dispersion pressure.
2.3.4 Preparation of Powdered and Nanocrystalline TiO2 by the

Sol-gel Method
The sol-gel technique enables one to synthesize highly pure and homogeneous
materials by starting from a colloidal suspension (sol) obtained from liquid
solutions of organometallic or inorganic precursors. The stability of a sol
suspension is due to van der Waals and coulombic repulsive strengths among
very small particles negligibly subjected to gravitational forces. The transfor-
mation of a sol into another phase (the gel) can be induced under various
experimental conditions. The gel is a macromolecular and highly viscous solid
that encloses molecules of solvent. By drying the gel it is possible to obtain
porous solids that usually are used to produce advanced materials (e.g.,
ceramics).
In a typical sol-gel process carried out to prepare TiO2, the sol is obtained by
hydrolysis and polymerization reactions of the TiO2 precursors that are gen-
erally organic titanium alkoxides (also metal inorganic salts can be used)
as tetra-n-butoxide or tetraisopropoxide dissolved in alcohol (2-propanol,
1-pentanol, ethanol, etc.). The latter are added to water [Equation (2.1)] to
induce hydrolysis to titanium hydroxide and the size of the TiO2 particles
depends on the experimental conditions used, such as for instance the ratio
between precursor and water, initial pH, reaction time, presence of foreign ions
and temperature:
Tiðiso OC3 H7 Þ4 þ 4H2 O ! TiðOHÞ4 þ 4C3 H7 OH ð2:1Þ
Polymerization and loss of solvent gives rise to the transition from liquid sol
into a solid gel phase. The formation of the Ti-O-Ti chains is facilitated by a
low content of water, low hydrolysis rate and excess of precursor in the reaction
ambient. The sol-gel method is a versatile approach to preparing TiO2 with
tailored morphological properties and the removal of the organic counterpart
from the TiO2 gels plays an important role in the preparation of TiO2 samples
with physicochemical features strictly related to their photocatalytic proper-
ties.14–22 A gelling process can be carried out by treating the reactant mixtures
under reduced pressure23 and/or by using various additives, such as HCOOH,
HO2CCO2H, CH3COOH, HCl, SnCl2, etc.24–28 Some additives can play the
role of chelating agents, others the role of hydrolysis catalysts (HCl or SnCl2).
In particular, the presence of appropriate chelating agents that modifies the
titanium alkoxide precursor allows one to control the hydrolysis and con-
densation reaction rate.
An example of the synthesis of TiO2 samples is reported in the following.
Titanium isopropoxide in 2-propanol was allowed to react with a stoichio-
metric amount of a chelating ligand (HCOOH or CH3COOH). Subsequently it
was hydrolyzed under strong acidic catalysis (HCl) or with water using SnCl2 as
the catalyst. The gelling process was carried out by either leaving the reactant
mixture in air or treating the pre-hydrolyzed solution under reduced pressure.
The addition of water gave rise to fine emulsions that turned into a clear
solution after ca. 1 day. The pre-hydrolyzed solution was divided in two parts:
the first was treated under reduced pressure until a granular gel was obtained,
while the second was left in the air at 298 K until a monolithic gel was obtained.
The latter was dried in the air for 7 days and then under vacuum for 2 days. The
samples obtained from ligand-modified Ti-alkoxide precursors were white
powders, whereas those prepared in the presence of SnCl2 were pale yellow
materials. The samples gelled under reduced pressure presented low values of
BET specific surface areas compared with those spontaneously gelled in the air,
due to the forced solvent evaporation from incompletely hydrolyzed titanium
oligomers. Both types of crude gels (vacuum or air gelled) were not satisfac-
torily crystallized and they were also subjected to a water reflux treatment or to
heating in air to obtain anatase (688–808 K), rutile (T4923 K) or mixed
48 Chapter 2
anatase–rutile phases. In some cases brookite phase appeared together with
anatase.
Notably, the photocatalytic activity of such TiO2 nanocrystalline samples
depended not only on the structural, intrinsic electronic and surface physico-
chemical properties of the samples but also on the possible presence of
adsorbed organic impurities, which had detrimental effects by poisoning the
catalytic sites. The most photoactive samples for photodegradation reaction
were those prepared in the presence of formic acid gelled spontaneously in air.
The reflux conditions reported in ref. 29, which describes the synthesis of
anatase nanoparticles, were a 16 h reflux process performed after precipitation
of a white precipitate consisting of amorphous particles. Subsequent cen-
trifugation, evaporation under reduced pressure at 313 K, and redispersion
in toluene gave rise to a sol of ca. 20 wt% of nanoparticles of titania with a
size of a few nanometers. The separated nanoparticles were mixed with
3,3,4,4,5,5,6,6,7,7,8,8,8,-tridecafluorooctyl-1,1,1,-triethoxysilane (FTS) in dry
methyl ethyl ketone to obtain a transparent binder, which is stable in a
refrigerator for at least 2 months, that can be used for the preparation of
photocatalytic coatings.
Other papers report the preparation of polycrystalline or nanostructured
TiO2 by using inorganic salts [TiCl3, TiCl4, Ti2(SO4)3, Ti(SO4)4] as the pre-
cursors and by carrying out the hydrolysis in water and ammonia30,31 or in pure
water.32,33
Pioneering studies on bare and iron-loaded TiO2 photocatalysts by Bickley
et al.30,31 have reported the preparation of polycrystalline TiO2 in the anatase,
rutile or anatase and rutile mixed phases using TiCl3 as precursor. The pre-
paration started with an aqueous solution of TiCl3 to which ammonia was
added dropwise at room temperature. The reaction products were allowed to
stand for 24 h in a vessel and subsequently the resulting solid was filtered off,
washed thoroughly with distilled water until it was free of residual Cl ions and
finally dried at 373 K for 24 h. Various portions of the obtained solid were
calcined for 24 h at 773, 923, 1073 and 1273 K. The presence of rutile phase
increased with increasing calcination temperature up to ca. 1273 K, at which
point only rutile phase was detected by X-ray diffraction measurements.
Another fundamental study32 deals with the preparation of some TiO2
samples both in the anatase and rutile phases by using TiCl3 or TiCl4 (ex TiCl3
or ex TiCl4) as the precursors. The method used to obtain the samples ex TiCl3 is
virtually identical to that employed in 30 and 31, whereas when TiCl4 was used
as the precursor it was allowed to react with pure water at ca. 278 K and the pH
was adjusted by NaOH up to 4.5. Notably, caution is needed in the last case
because the reaction is strongly exothermic and gaseous HCl is released. The
subsequent procedure was the same as described above for samples ex TiCl3.30,31
Both samples ex TiCl3 and ex TiCl4 were tested to carry out the photo-
degradation of phenol in aqueous medium as a probe reaction. The physico-
chemical features as determined by the preparation methods affect the
photocatalytic behavior in addition, of course, to the semiconducting proper-
ties. Rutile phase was active or inactive according to the preparation
conditions; in particular, it was completely inactive only when prepared by
calcining at relatively high temperatures (T4973 K) and for long times (t43 h).
The most photoactive samples were those ex TiCl4 that were prepared by cal-
cining 336 h at 823 K, or 24 h at 873 K.
The improved crystallinity beneficially influenced the photoreactivity, but
the presence of surface hydroxyls and the particle size also appeared to be
essential factors. A compromise between these properties seems to be essential
to guarantee an appreciable photoactivity. Irreversible dehydroxylation, the
extent of which depends on the temperature and time of calcination, indeed,
does not favor the adsorption of O2 onto the TiO2 surface. The photoreduction
of O2(ads) by electrons produced under illumination in the conduction band is in
principle possible on both TiO2 modifications. O2 (ads) species may evolve in
various ways, producing further oxygenated species involved in the photo-
oxidation of the organic molecules. On the other hand, the oxidative processes,
which involve the photogenerated holes and adsorbed phenolic species as well
as OH groups, have similar driving forces on anatase and rutile. Therefore,
the photooxidative degradation processes, from a thermodynamic point of
view, should occur for both anatase and rutile.
Consequently, the differences in photoactivity reported in the literature often
do not depend very strongly on the intrinsic electronic characteristics of the two
phases, although the electron–hole recombination rate of rutile phase has been
reported to be higher than that of anatase,32,34 but mainly on the surface
physicochemical properties of the samples.
The influence of one or many of these surface properties can be more or less
significant, depending on the type of molecule to be photodegraded, on the pH
of the medium, the irradiation intensity, etc. Consequently, it is not easy to
straightforwardly correlate all these factors with the photoreactivity, since
interplay between them and the redox reactions takes place, which sets the final
level of photoreactivity.
2.3.5 Preparation of Nanoparticles, Nanorods, Nanotubes and

Nanowires of TiO2 by the Hydrothermal Method
Hydrothermal syntheses of TiO2 nanoparticles35–44 or nanorods45 are carried
out in water or in mixtures water/ethanol and, generally, steel pressure auto-
claves are used, with the possibility of controlling temperature and pressure.
In ref. 44 the TiO2 nanoparticles were prepared by adding dropwise titanium
tetraisopropoxide to a water/ethanol solution at pH 0.7 (adjusted with HNO3)
and allowing the reaction to occur at 153 K for 4 h. The size of the anatase
particles obtained in such a way ranged between 7 and 25 nm, depending on the
concentration of the precursor and the composition of the mixed water/ethanol
solvent. Nanorods were obtained, instead, by treating a dilute aqueous solution
of TiCl4 at 606–696 K for 12 h in the presence of acids or inorganic salts.45
Some authors tune the morphology of the resulting nanorods by using additives
or changing the experimental conditions.46–48
50 Chapter 2
TiCl4
Hydrolysis
Route 1:(TiCl4:H2O ratios Route 2:(TiCl4:H2O ratios
From1:1 to 1:10 v/v) From 1:25 to1:100 v/v)
Route 1b:
Gel Solution Dispersion
Dispersion
Dialysis of
1:10 (v/v) samples
Calcination Route 1a:
Suspension +H2O to obtain
Route 1: Boiling for
good
with good TiCl4: H2O ratios
Boiling for 2h
photoactivity from 1:25 to 1:100
2h
then 2h boiling
Dispersion with Suspension with

high photoactivity Route 3: high photoactivity Suspension with
Suspension with
and low Cl- Dialysis and high Cl - low photoactivity
low
concentration concentration
Scheme 2.1 Preparation procedure of nanostructured TiO2 samples obtained by

hydrolysis of TiCl4, as described in ref. 50.
Other papers49–51 report the use of TiCl4 as precursor to obtain nanoparticles

of TiO2 under experimental milder conditions than those reported above that
employed hydrothermal processes in a closed vessel at higher pressures than 1
atm. Scheme 2.1 sketches the procedure followed to obtain the samples
described in ref. 50, and Figure 2.2 shows XRD diffractograms of some
samples.
In these papers the photoactivity mainly depended on a compromise between
crystallinity and particle size. In fact, the beneficial role of an increased crys-
tallinity contrasts with the detrimental effect due to the corresponding increase
of particle size. The most active samples prepared by using a TiCl4/H2O ratio
equal to 1 : 50 just matched the highest crystallinity and the lowest particle size.
Notably, the nanostructured TiO2 catalysts were more efficient than Degussa
P25 at pH 2. The activity of the catalysts was enhanced by dialyzing the sus-
pensions against water. The technique presented seems an economical and fast
way to prepare active photocatalysts. Limitations are expected for their use in
solar reactors due to the slight shift (quantum size effect) in the band gap of the
samples whose diameter range between ca. 10 and 45 nm.
More recently nanocrystalline anatase, rutile and brookite TiO2 powders
have been prepared by thermohydrolysis starting from TiCl4 in HCl or NaCl
solutions.52,53 Reference 52 reports that rutile, mixtures of brookite and rutile
or mixtures of anatase, brookite and rutile were obtained depending on the
acidity of the medium. Mixtures of brookite and rutile were prevalently
obtained when the hydrolysis of TiCl4 occurred in diluted HCl. Ternary mix-
tures of anatase, brookite and rutile were always formed in NaCl solutions.
Figure 2.2 (I) XRD patterns of samples prepared with various TiCl4/H2O ratios: (a)
1 : 1, (b) 1 : 10, (c) 1 : 50, dialyzed, (d) 1 : 50 and (e) (1:100). A: anatase,
R: rutile. (II) XRD patterns of powders obtained by drying or calcining
the gel (Route 1b in Scheme 2.1): (a) 298, (b) 673, (c) 773 and (d) 873
K. A: anatase, R: rutile. (Reproduced with permission from ref. 50).
Pure brookite nanoparticles were separated from rutile by simple peptization

with water by slightly modifying the method reported in ref. 54, where the
peptization was performed by using HNO3. 4-Nitrophenol photodegradation
was used to evaluate the photocatalytic activity of the various samples. The
highest activity corresponded to powders consisting of more than one crys-
talline phase. The effects of phase composition and characterization of the
photocatalysts were studied in more detail in ref. 53. The most efficient samples
consisted of a ternary mixture of anatase, brookite and rutile and the presence
of brookite phase did not seem to negatively influence the photoreactivity.
Some powders were more active than Degussa P25.
Some photoelectrochemical measurements53 performed according to the
method reported in ref. 55 have allowed determination of the position of the
flat band potential and the valence and conduction bands of the three poly-
morphic phases (Figure 2.3).
Notably, the experimental flat-band potential of pure brookite ( 0.46 V),
reported for the first time in ref. 53, is very close to the 0.44 V calculated by
Grätzel and Rotzinger by means of extended Hückel molecular orbital (MO)
calculations.56
TiO2 brookite phase has been used less frequently in photocatalysis than the
anatase and rutile phases because it is obtained as a mixture with one or both of
52 Chapter 2
Figure 2.3 Band edges (versus NHE) at pH 7 of rutile, anatase and brookite samples.
(Reproduced with permission from ref. 53.)
the other phases and its separation implies an additional peptization process as
above reported.53,57
Moreover, the interpretation of XRD diffractograms is not easy when the
brookite phase is present together with the anatase. In fact the main (101)
diffraction peak of anatase at 2y ¼ 25.281 overlaps with the (120) and (111)
peaks of brookite at 2y ¼ 25.341 and 25.691, respectively. Therefore, it is
advisable to use Raman spectroscopy to demonstrate unequivocally the com-
plete absence of anatase phase, by checking the absence of anatase character-
istic peaks at 391 and 510 cm1.57
Figure 2.4 shows some XRD diffractograms of brookite, and brookite–rutile
mixtures before their separation, while a representative Raman spectrum of the
pure brookite phase is given in Figure 2.5.
Very recently a set of papers has reported the preparation under very mild
conditions of badly crystallized nanocrystalline TiO2 anatase, brookite and
rutile phases that were more selective than Degussa P25 (ca. 30% rutile, 70%
anatase) and Merck (anatase) commercial samples for the photooxidation in
water of some aromatic alcohols (benzyl, 4-methylbenzyl, 4-methoxybenzyl
and 4-nitrobenzyl alcohols) to the corresponding aldehydes.57–63 The photo-
catalysts were prepared by hydrolysis of TiCl4 in water at room temperature.
Scheme 2.2 reports the synthesis of brookite and rutile TiO2 by hydrolysis of
TiCl4 in HCl aqueous solution.
The most selective samples to aldehyde (up to 72% mol with respect to the
transformed alcohol) were rutile samples prepared under very mild conditions
at room temperature from TiCl4.61
A comparative ATR-FTIR study of selected laboratory prepared photo-
catalysts and Degussa P25 has been reported63 together with the determination
Figure 2.4 XRD diffractograms of (a) brookite–rutile mixture, (b) pure rutile, (c)
pure brookite and (d) calcined brookite (723 K, 2 h). (Reproduced with
permission from ref. 57.)
Figure 2.5 Raman spectrum of a representative sample of pure TiO2 brookite.

54 Chapter 2
Brookite-rutile mixtures easily separable

areare
obtained in in
obtained diluted HCl after refluxing for
diluted
various times
The clear supernatant is separated and water is added.

The procedure is repeated twice
Drying of the Withdrawal of the Recovery ofthe

Recover of the
solid-liquid supernatant dispersion sedimented solid
mixture
Drying
Drying
Mixtures
Mixtures Pure
Pure Pure
Pure
RR-B
-B Brookite
Brookite
Rutile
Rutile
Scheme 2.2 Synthesis of brookite and rutile TiO2 by hydrolysis of TiCl4 in HCl
aqueous solution.57–63
of their main photoelectrochemical properties (band gap, conduction and

valence band edges) by means of the method reported in ref. 55. The band gap,
valence band and conduction band edges were almost identical for all of the
laboratory prepared samples in which anatase phase was predominant, although
the samples showed a different selectivity to aldehydes. Conversely, appreciable
differences were noticed for laboratory-prepared samples containing other
phases. The ATR-FTIR results showed a very dissimilar hydrophilicity
(Degussa was more hydrophobic than the laboratory-prepared samples) and
different ability for adsorbing the organic compounds deriving from benzyl
alcohol photocatalytic oxidation. These results indicate that for selective pho-
tooxidation of alcohol to aldehyde, analogously to the photomineralization
reactions, the surface physicochemical properties should be considered because
they could play a more important role than the intrinsic electronic properties.
Preparation of mesoporous TiO2 microspheres with sizes ranging between 5
and 30 mm starting from Ti2(SO4)3 industrial grade (16.9 wt%) was also
reported.64 The microspheres could be used as photocatalyst in fluidized bed
reactors to treat waste water. They were prepared as follows: blue Ti(OH)3 was
obtained by injecting contemporaneously Ti2(SO4)3 and NH4HCO3 solutions
via two syringe pumps into a reactor containing distilled water under vigorous
stirring. The pH value was maintained at 6.5–7.0 by adjusting the flux of
ammonium hydrogen carbonate to guarantee the complete precipitation of
Ti31 ions. The precipitate was filtered off, washed with distilled water and dried
at 373 K for 12 h to be transformed into TiO2 microspheres. Different fractions
of them were finally subjected to calcinations at 773, 873, 973, 1073 or 1173 K
for 2 h in air. XRD data indicated that the microspheres were all amorphous
when the calcination temperature was below 773 K, while relatively broad
diffraction peaks due to anatase phase were present for the materials calcined at
873–1073 K. The crystallite sizes, determined by using the Scherrer equation,
increased by increasing the calcination temperature, and they ranged between
ca. 7 and 35 nm. The samples calcined at 1173 K showed the presence of the
rutile phase in addition to the anatase phase.
According to calculations, the TiO2 sample calcined at 1173 K was a mixture
of rutile 29.6% and anatase 70.4%, which is similar to Degussa P25. In addi-
tion, the phase transformation from anatase into rutile in TiO2 materials did
not occur during calcination below 1073 K and, consequently, only the anatase
phase was present at 1073 K, some 100–200 K higher than the reported phase
transformation temperatures.65,66 This shows that the thermodynamic phase
stability can be dependent on particle size, and in particular the anatase
structure proved to be thermodynamically more stable than the rutile one for
particle sizes of ca. 14 nm.67 The latter value is similar to the crystal sizes of the
sample calcined at 1073 K.
The hydrothermal method has also been used to prepare TiO2 nanorods
(Figure 2.6),45 nanotubes (Figure 2.7)68–73 and nanowires (Figure 2.8).74,75
TiO2 nanotubes have been reported to be obtained from TiO2 powders held
at 293–383 K for 20 h in an autoclave in an aqueous solution of NaOH (2.5–
20 M).68 It is, however, necessary to wash the products with HCl aqueous
solution and water. It has been hypothesized that some of the Ti–O–Ti bonds
break in the presence of NaOH, with resultant formation of Ti–O–OH and Ti–
ONa bonds and the subsequent formation of nanotubes after the acid
treatment.
Figure 2.6 TEM photograph of TiO2 nanorods obtained by the hydrothermal

method. (Reproduced with permission from ref. 45.)
56 Chapter 2
Figure 2.7 TEM photograph of TiO2 nanotubes. (Reproduced with permission from
ref. 71.)
Figure 2.8 TEM photograph of TiO2 nanowires. (Reproduced with permission from
ref. 76.)
TiO2 nanowires have been prepared from layered titanate particles using the
hydrothermal method.75 The layered structured Na2Ti3O7 was treated with
HCl (0.05–0.1 M) at 413–443 K for 3–7 days in an autoclave and subsequently
the product was washed with water. Before the formation of nanowires, steps
involving exfoliation of layered Na2Ti3O7 and the formation of nanosheets
occurred.
2.3.6 Solvothermal Method

The solvothermal method differs from the hydrothermal method in that a non-
aqueous solvent it is used. Higher temperatures can be achieved because many
organic solvents with boiling points higher than that of water can be chosen.
Their use allows a better control of size and shape distributions of the TiO2
nanoparticles, nanorods or nanowires.76–80
In ref. 80 titanium tetraisopropoxide was mixed with toluene (weight ratio 1–
3 : 10) for 3 h at 523 K. The average particle size of TiO2 powders increased by
increasing the composition of titanium tetraisopropoxide, but no TiO2 was
produced at 1 : 20 and 2 : 5 weight ratios.
Surfactants have been used to synthesize TiO2 nanoparticles or nanorods
with narrow size distribution.76,79 In ref. 79 titanium tetraisopropoxide, dis-
solved in anhydrous toluene in the presence of oleic acid as the surfactant, was
kept for 20 h at 523 K in an autoclave without stirring. Nanorods were formed
in the presence of a sufficient amount of titanium tetraisopropoxide or sur-
factant. The diameter and length of these nanorods were 3–5 nm and 18–25 nm,
respectively, depending on the ratio precursor/surfactant and precursor/
solvent.
The solvothermal method was also used to prepare nanowires in the same
way as with the hydrothermal method.81,82 In ref. 81 a TiO2 suspension in 5 M
NaOH water–ethanol solution was kept in an autoclave at 443–473 K for 24 h.
TiO2 nanowires were obtained after the product was cooled at room tem-
perature, washed with a dilute HCl aqueous solution and dried at 333 K for
12 h in air. The type of solvent influenced dramatically the crystal morphology.
In the absence of ethanol, for instance, flake-like structures of TiO2 were
obtained, whereas in the presence of chloroform TiO2 nanorods were produced.
2.3.7 Sol Method

This method is a nonhydrolytic sol-gel process and generally involves the
reaction of TiCl4 (or other halides) with different oxygen donor species, such as
organic ethers or metal alkoxides:83,84
TiCl4 þ 2ROR ! TiO2 þ 4RCl ð2:2Þ
TiCl4 þ TiðORÞ4 ! 2TiO2 þ 4RCl ð2:3Þ
In ref. 83 metal alkoxides were allowed to react for no longer than 5 min with
a hot solution of TiCl4 mixed with trioctylphosphine oxide in heptadecane at
573 K under inert gas atmosphere. The size of the particles was not affected by
the type of alkyl substituent, R, whereas the reaction rate increased upon
increasing the branching of R.
58 Chapter 2
Various titanium halides were tested in addition to TiCl4 and the particles size
ranged from 9.2 nm for TiF4 to 3.8 nm for TiI4, indicating that the size of the
formed nanocrystals of anatase decreased upon increasing the size of the halide.
In ref. 84 the reaction between TiCl4 and benzyl alcohol was performed at
313–423 K for 1–21 days. The product was washed and subsequently calcined
at 723 K for 5 h. The particle size depended strongly on temperature and on the
concentration of TiCl4. In particular, particles in the range 4–8 nm were
obtained by choosing appropriate thermal conditions and the concentration of
TiCl4. Moreover, an almost uniform size and shape of the particles was
observed at low temperatures (e.g., 313 K).
In the presence of surfactants, TiO2 nanorods of different size and shape
were synthesized.85–90 The preparation started with the hydrolysis under
nitrogen flow of titanium tetraisopropoxide in oleic acid at 353–373 K for
5 min. To this solution a 0.1–2 M aqueous base solution was added rapidly and
then the mixture was mixed for 6–12 h. Some of the bases used were tri-
methylamine, trimethylamino-N-oxide, triethylamine, tributylamine, tetra-
methylammonium hydroxide and tetrabutylammonium hydroxide.
2.3.8 Laser Pyrolysis Method

IR laser pyrolysis has been employed successfully as a single-step reaction route
for the synthesis of anatase/rutile mixed nanopowders. Sensitized mixtures
containing TiCl4 (vapor) and air as gas-phase precursors were used and mixed
crystallographic phases of TiO2 (rutile and anatase, 20 and 30 nm mean dia-
meter, respectively) were obtained. TiO2 nanopowders with ca. 90% anatase
content were obtained at a high concentration of air.91,92
Another paper93 reports the synthesis of TiO2 powders with an average
diameter as low as 8 nm by laser pyrolysis by using an aerosol of titanium
tetraisopropoxide as the main precursor sensitized by C2H4. The possibility of
controlling the anatase/rutile phase ratio was demonstrated over a large range
by tuning the experimental parameters.
Samples prepared by using laser radiation usually appear to be less porous
materials.
2.3.9 Microwave Method

It is possible to use microwave radiation to prepare TiO2 nanomaterials.94–97 In
ref. 94 high quality rutile TiO2 nanorods were prepared by means of a micro-
wave hydrothermal method, while ref. 95 describes the preparation of nano-
tubes between 8 and 12 nm diameter and up to 200–1000 nm long. TiO2
nanotubes formed solely by microwave irradiation of NaOH aqueous solutions
contained anatase, rutile or both phases.
Corradi et al.96 have reported the rapid preparation (5 min to 1 h) of nano-
particle suspensions of TiO2 with microwave radiation, whereas 32 h was
needed for a conventional hydrothermal synthesis at 468 K.
97
More recently, Addamo et al. have presented a very simple procedure to
prepare anatase, rutile or mixed phase TiO2 photocatalysts by microwave
irradiation at low temperature. The samples were active for 4-nitrophenol
photodegradation in aqueous solution and 2-propanol photooxidation in a
gas–solid system. The starting materials were unusual TiO2 gels formed from
TiCl4. The use of microwaves for very short times enhanced the TiO2 crystal-
linity, preventing an increase of particle size and minimizing the decrease of
specific surface area. The particle size ranged between 16 and 25 nm, depending
on the treatment temperature (393 or 423 K) and time (15, 30 or 60 min). The
most active sample was prepared by irradiating for 30 min at 423 K the gel
obtained from a 1 : 10 TiCl4 : H2O (v/v) solution. For this last sample the
observed initial reaction rate of 4-nitrophenol photodegradation was 93 109
versus 50 109 mol l1 s1 determined when TiO2 Degussa P25 was used. A
relatively low efficiency for the photooxidation of gaseous 2-propanol was
obtained, though, due to the large amount of water present in the gel, which
reduces the number of active TiO2 surface sites.
2.4 Preparation of Films

Research on the preparation, characterization, and testing of films (thickness
ranging from a few nanometers to ca. 100 mm) constituted by many kinds of
insulator and semiconducting materials has attracted great attention among the
scientific community because these devices are widely used in micro- and
optoelectronic industries.
Some types of films can be used in devices (sensors) that provide information
on the occurrence of some phenomena by exploiting thermal, biological,
optical, magnetic, etc. effects. Many, for instance, are very important in the
field of environmental chemistry, allowing the detection of noxious gases. This
chapter does not aim to report general information on the numerous typologies
of existing films;98–102 instead, only some methods suitable for preparing
photocatalytic TiO2 films are presented.
2.4.1 Wet Coating Technologies to Prepare TiO2 Films

These technologies have been developed for various types of supports, but
mainly for glasses. Both the wet coating materials and the equipment are not
standardized and therefore they have been tested and developed by the users.
Transparent and non-transparent coated materials can be obtained, depending
on the experimental conditions employed. Examples are glasses with antifog-
ging, conductive and photocatalytic properties, although to choose the wet
coating technique for large area or wide volume applications is not opportune
because other techniques that will be illustrated below (see for instance mag-
netron sputtering) are more convenient. Wet coating techniques, however,
often appear cost-effective and can be divided basically into two categories: the
first implies a heating treatment after the coating step at temperatures generally
60 Chapter 2
ranging between 423 and 823 K, depending on the support used and on the
TiO2 phase that it is expected to form, while the second involves an UV or IR
treatment. In the second case, unlike the first, the chemical structures obtained
in the liquid coating material do not change.
Notably, the coating step has to be performed onto a cleaned surface and
under clean room conditions.
In the following, only dip-coating, spin-coating, flow coating, (plasma) spray
drying and spray-pyrolysis methods will be presented as they have been selected
very often for the preparation of TiO2 photocatalytic films. In most cases the
obtainment of TiO2 photoactive films requires a heating post-treatment
because the precursor species – which are generally dissolved (usually as tita-
nium alkoxides or titanium chlorides) in alcoholic solution or are present as a
sol or a not highly viscous gel in aqueous or alcoholic suspension (due to the
occurrence of a pre-hydrolysis process) – need to be transformed into nano-
crystalline TiO2 after their contact with the surface of the support.
2.4.1.1 Dip Coating

Dip-coating is carried out by first immersing the support in a liquid, in which
the precursor is present, and then withdrawing it at controlled speed and
temperature under atmospheric conditions (Figure 2.9).
This process has been developed both for flat and curved surfaces, but a
drawback is the difficulty encountered in coating large surfaces. An old coating
process that has been used to produce colored glasses in the crystal industry
implies the dipping of an uncolored glass into a melt colored glass with similar
chemical composition before it is blown to the desired shape.
Dip-coating technology has been used for plate glass, solar energy systems,
anti-reflective coatings on windows, optical filters, dielectric mirrors, photo-
catalytic films, etc.103–111
It is possible to obtain coating thicknesses from few nanometers to 1 micron
with high precision by selecting a suitable viscosity of the coating liquid and
withdrawal rate, in accord with the Landau–Levich equation:112
0:94ðm UÞ2=3
t¼ 1=6
ð2:4Þ
gLV ðr gÞ1=2
where t is the coating thickness, m the viscosity, U the withdrawal rate, gLV the
liquid–vapor surface tension and r the solution density.
The Landau–Levich equation can be applied only when U41 mm s1; it
cannot be applied to systems in which the particles repel each other.
The atmosphere controls the evaporation of the solvent and the subsequent
transformation of the sol into the film. Moreover, the thickness of the layer
depends on the dipping angle between the support and the liquid surface and
different thicknesses of the layer can be produced at the top and bottom sides of
the surface that has been coated.113
Dipping Wet layer formation Solvent evaporation

(A)
(B) (C)
Figure 2.9 (a) Steps of the dip coating process: (i) dipping of the support in the
coating liquid, (ii) formation of the wet layer by withdrawing and (iii)
evaporation of the solvent; (b) formation of the film on the substrate; (c)
apparatus for dip coating. [(b) Photograph courtesy of www.advanced-
materials.at/rd/rd_seg_en.html. (c) Photograph courtesy of http://
www.engineerlive.com/ChemicalEngineer/Materials/Precision_dip_
coating_for_the_fabrication_of_thin_films/21225/.]
62 Chapter 2
Figure 2.10 Low-angle XRD diffractogram of a 15 cycle deposited TiO2 film.

Reference 107 reports the preparation of photocatalytic TiO2 films by the dip-
coating technique by using sols derived from titanium tetraisopropoxide on glass
substrates previously covered by a SiO2 layer obtained from a tetraethyl
orthosilicate sol. The films, after thermal treatment at 673 K, mainly consisted of
TiO2 anatase with a small amount of rutile (Figure 2.10). The calcinations were
carried out either step-by step or only at the end of the various dip coating steps.
The films subjected only to a final post-deposition calcination were thinner,
probably due to a sintering effect involving the whole mass of TiO2 (154 versus
252 nm for the 15 cycle deposited TiO2 film). The adherence was excellent, unlike
that of a similar film (easily detached by wiping) prepared by coating with TiO2
Degussa P25 suspended in water. The samples were tested under UV illumina-
tion by using as probe reaction the photooxidation of 2-propanol in the gas–
solid regime in the presence of water vapor; the results indicated a satisfactory
efficiency (initial reaction rate, r0, in the range ca. 6–24 109 mol l1 s1), with
CO2 and propanone being the only compounds detected.
The laboratory-made experimental set-up used to carry out the experimental
runs is sketched in Figure 2.11, while Figure 2.12 shows photoreactivity results
of a selected experiment.
Photoactive films consisting of pure anatase, brookite or rutile have been
prepared108 by dip coating from water dispersions obtained by using TiCl4 as
the precursor (Figure 2.13). Also in this case, the photodegradation of 2-
Figure 2.11 Set-up used for the photocatalytic degradation of 2-propanol. (Repro-
duced with permission from ref. 107.)
Figure 2.12 2-Propanol (K) and propanone (m) concentrations versus irradiation time.
Sample: TiO2 film deposited by 15 cycles and calcined after each deposi-
tion. Reaction temperature: 310 K; water vapor concentration: 1.4 mM;
irradiance: 1.3 mW cm2. (Reproduced with permission from ref. 107.)
64 Chapter 2
Figure 2.13 XRD patterns of TiO2 films, deposited in ten steps, constituted of pure
brookite, anatase and rutile phases. (Reproduced with permission from
ref. 108.)
propanol was used as probe reaction and the brookite film was shown to be
more efficient (Figure 2.14) than the anatase one, although a strict comparison
between the photoreactivity results cannot be performed because the mor-
phology and the thickness of the films were different.
2.4.1.2 Spin Coating and Flow Coating

The spin coating technique is usually employed to prepare films onto flat sur-
faces, although a homogeneous coating can also be obtained with non-planar
substrates. The solution or the sol is placed onto the substrate to be coated and
then rotated at high speed to spread it by centrifugal force. During the spinning
step, evaporation of the solvent and gelation can occur. The thickness of the
coating varies between some hundreds nanometres and ca. 10 mm, depending
on the duration and the rate (usually ranging between 500 and 10 000 rpm) of
the spinning (Figure 2.15).
The quality of the coating depends on the rheological parameter of the fluid
used to coat. In principle, one should operate in the Newtonian regime and an
important parameter to be considered is the Reynolds number of the
Figure 2.14 2-Propanol degradation versus irradiation time in the presence of ten-
step deposited films: (’) pure anatase, (E) pure brookite and (m) pure
rutile. Initial 2-propanol concentration: 60 mM. (Reproduced with per-
mission from ref. 108.)
atmosphere around the sample. A high Reynolds number could be responsible

for turbulence and bad quality of the layer.
The film thickness can be correlated with the angular velocity, the solvent
evaporation rate and the viscosity of the fluid by using the following Meyer-
hofer equation:114

rA 3mm 1=3
t¼ 1 ð2:5Þ
rA0 2rA0 o2
where t is the final thickness, rA the density of the volatile solvent, rA0 the
initial value of rA, m the viscosity, m the evaporation rate of the solvent and o
the angular speed.
A simpler equation can be used [Equation (2.6)]:
t ¼ A oB ð2:6Þ
where A and B must be empirically determined. Results reported in 115 and 116
concerning the thickness of films obtained by spin coating at different angular
speeds fit Equation (2.6) well and B ranges between 0.4 and 0.7.
Examples of preparation of TiO2 or TiO2 composite films have been reported
in the literature.117–120 Reference 117, for instance, deals with the preparation
and testing of TiO2–methylcellulose (MC) nanocomposite films. A sol sus-
pension was prepared by adding titanium tetraisopropoxide (TTP) to a mixture
of ethanol and HCl (molar ratio TTP : HCl : EtOH : H2OQ1 : 1.1 : 10 : 10) and
66 Chapter 2
(A)
(B)
Figure 2.15 (a) Steps of the spin coating process: deposition of the fluid, spinning
and evaporation/gelation of the solvent; (b) typical apparatus for
spin coating. (Photograph courtesy of www.mbraun.com/oled-process-
spincoater.htm.)
then adding a 2 wt% solution of methylcellulose. A TiO2 nanopowder
was dispersed in the sol and a microscope glass slide was coated with the
mixture by using the spin coating technique. The presence of MC, acting
as a dispersant agent, avoided problems due to film inhomogeneity and
defects that could cause peeling and cracking during calcination carried out up
to 773 K. Photocatalytic activity of the composite film was evaluated by
degrading a textile dye, i.e. Light Yellow X6G (C.I. Reactive Yellow 2), as a
model pollutant, and it was compared with the activity of (i) a similar com-
posite film without MC and (ii) a TiO2 nanopowder. The good mechanical
integrity makes this composite film an interesting candidate for practical
applications.
Nanoscale composite TiO2–SnO2 thin films with different ratios have been
deposited from sol-gel TiO2–SnO2 mixtures on quartz substrates by spin
coating.119 XRD and AFM experiments showed that smooth and uniform
anatase, anatase–rutile as well as rutile structural thin films were
formed at 273 K, depending on the Sn ratio. Nanocomposite films with
a Ti : Sn ratio of 3 : 1 showed excellent photocatalytic activity in the UV–Vis
region.
The flow coating process is not usually employed for the preparation of TiO2
films because it is not easy to obtain uniform layers by this method (the coating
thickness increases from the top to the bottom of the substrate), unless it is not
coupled with a spinning process. The coating thickness depends on the incli-
nation angle of the substrate, on the solvent evaporation rate and on the
viscosity of the fluid used (Figure 2.16).
Fluid (sol)
Substrate
Coating
Bath
Figure 2.16 Sketch of a typical flow-coating apparatus.

68 Chapter 2
2.4.1.3 (Plasma) Spray Drying
The use of this process allows films to be obtained by spraying and drying a
slurry that contains dispersed TiO2 particles.121–127 This method, which is
suitable to be industrially scaled up, offers advantages since it is ca. ten-times
faster than the dip coating technique, although the films usually show poor
mechanical properties. When plasma spray drying is used, a feedstock material
is melted and sprayed onto a substrate where its solidification occurs with the
consequent formation of a film.
TiO2 coatings with a mixture of anatase and rutile phases have been obtained
by plasma spraying using a spray-dried powder as feedstock material.124,125
The characteristic of the formed layer depended not only on the parameters of
the process but also on the type of feedstock material. Figure 2.17 shows a
plasma-spray experimental set-up.
In ref. 126 nano-TiO2 photocatalytic coatings were obtained on stainless
steel by an atmospheric plasma spraying process. The starting nano-TiO2
powder, consisting of 100% anatase phase, was agglomerated by the spray
drying process. The photodecomposition efficiency of the TiO2 coatings was
evaluated by the kinetics of decomposition of the methylene blue in aqueous
solution. The best photodecomposition efficiency was observed when TiO2
coatings were prepared under a lower heat input, resulting in higher anatase
phase fraction and smaller anatase grain size.
In a comprehensive comparative study127 on the microstructure and pho-
tocatalytic performances of TiO2 coatings obtained by various thermal spray-
ing methods it is reported that the crystalline structure depends strongly on the
technique of thermal spraying deposition. Agglomerated spray dried anatase
TiO2 powder was used as feedstock material for spraying. The photocatalytic
behavior of the TiO2-base surfaces was evaluated from the conversion rate of
gaseous nitrogen oxides (NOx). A high amount of anatase was suitable for the
photocatalytic degradation of the pollutants. Suspension plasma spraying
allowed the retention of the original anatase phase.
Compressed air
Suspension
Atomizer
Pump
Torch
Substrate
Feedstock suspensions
Figure 2.17 Example experimental set-up used for the plasma-spray technique.
2.4.1.4 Spray Pyrolysis
The spray pyrolysis method is based on the pyrolytic decomposition of an
inorganic or organic precursor of the film dissolved in solution. A spray nozzle,
with the help of carrier gases, gives rise to the formation of fine drops (aerosol)
from the solution. The temperature of the substrate is maintained at a constant
value by using a furnace or a hot plate. The best conditions for the preparation
of the film occur when the droplets approach the substrate just before complete
elimination of the solvent. Films grown at a substrate temperature less than
573 K are generally amorphous or badly crystallized. To obtain polycrystalline
films, one needs to employ either higher temperatures or a post-annealing
treatment.128–130
Figure 2.18 shows a sketch of a spray pyrolysis set-up.
TiO2 films have also been prepared and characterized by spray pyrolysis.131–136
In some cases the photocatalytic activity has been tested.
The photoelectrochemical behavior of type 304 stainless steel (SUS 304)
coated with a TiO2 thin film with the aim of photoprotecting the material from
cathodic corrosion has been studied under different experimental conditions.131
The photo-potential of TiO2-coated SUS 304 was, for example, –350 mV vs.
Ag/AgCl in an aerated aqueous solution containing 3 wt% NaCl (pH 7) under
illumination with 10 mW cm2 ultraviolet (UV) light, which was more negative
Solution
Substrate
feeding
holder
Flame
Air Atomizer
Recycled
solution
Pilot
flame
torch
MFC MFC MFC
O2 C2H2
Figure 2.18 Sketch of a spray pyrolysis set-up.

70 Chapter 2
than the corrosion potential of the bare steel ( 100 mV). Moreover, bleaching
of methylene blue dye on TiO2 thin film-coated SUS 304 was observed under
1 mW cm2 UV illumination, indicating the possibility of photocatalytic self-
cleaning effects.
Hydrophilic TiO2 films have been synthesized from TiCl4 by spraying a sol
on glass substrates. The hydrophilic properties of the films were investigated by
contact angle measurements under UV light illumination.133
Transparent TiO2 thin films prepared on glass substrates were amorphous up
to a deposition temperature of 723 K. The crystallization process to anatase
phase started at ca. 823 K. These quite homogeneous and porous films were
photocatalytically active and the photooxidation of methanol to methanal in
water was successfully carried out.134
TiO2 thin films have been formed both by spray pyrolysis and DC magnetron
sputtering (see below) methods onto glasses that were coated with fluorine-
doped tin oxide (FTO).136 The films were characterized by X-ray diffraction,
scanning electron microscopy, atomic force microscopy and UV–visible spec-
troscopy. The influence of the total pressure of an Ar–O2 mixture on the
deposition rate, phase composition, crystallinity, surface morphology and pho-
tocatalytic properties was investigated for films deposited using the sputtering
technique. Transparent films were prepared by spray pyrolysis at low con-
centrations of titanium precursor. The photocatalytic properties of TiO2 thin
films were tested by using the degradation of methylene blue under UV light
irradiation as probe photoreaction. The highest degradation rates were observed
for films prepared by spray pyrolysis with a substrate temperature close to 673 K.
2.4.2 Physical Vapor Deposition (PVD) Techniques

This coating method involves purely physical processes rather than a chemical
reaction at the surface to be coated such as in chemical vapor deposition (CVD,
see next section). Physical vapor deposition (PVD) includes methods that allow
deposition of thin films by condensation of a vaporized form of the material
onto various surfaces.
Some examples of PVD techniques are (i) vacuum evaporation–deposition,
(ii) electron beam physical vapor deposition, (iii) sputtering deposition, (iv)
cathode arc (plasma) deposition and (v) pulsed laser deposition.
2.4.2.1 Vacuum Evaporation–Deposition

The vacuum evaporation–deposition technique is a convenient, simple and
widely used deposition method. The method implies the evaporation in low
vacuum of a material that condenses onto a substrate. The material to be
deposited is electrically heated to obtain the vapor pressure (generally ca. 105
Torr) needed for the evaporation process. The substrate is kept at a tempera-
ture that depends on the required properties of the film. The distance between
the substrate and the source is ca. 10–50 cm. After transition into the gaseous
Deposit
Evaporated
material
Heated coating
material
Vacuum
Figure 2.19 Sketch of a vacuum evaporation–deposition set-up.
state of the solid or liquid material to be deposited and the transport of vapor
from the source to the substrate, the condensation of the vapor occurs with
formation of the film (Figure 2.19).
Amorphous TiO2 films were vacuum-deposited on rock salt at room tem-
perature by evaporating small quantities (4–6 mg) of powdered anatase TiO2.
The films crystallized in anatase and rutile forms when they were irradiated by
an intense electron beam.137 Electron microscopy and electron diffraction
studies were performed on these films: rutile crystallites were small granules,
whereas anatase crystals grew to occupy larger areas of several microns in
linear dimension. The structural difference of the crystallized films seemed to
depend on the intrinsic properties of the amorphous films. The generation of
dislocations that constituted small angle grain boundaries was observed in
growing anatase crystals. In these crystals, twins were formed on the (112)
planes and dislocations were also observed in the individual grains.
In another paper138 anatase TiO2 thin films were prepared with deposition
rates equal to 16 nm min1 by a vacuum arc-plasma evaporation (VAPE)
method using sintered TiO2 pellets as the source material (Figure 2.20). The
films appeared to be highly transparent at substrate temperatures from room
temperature to 673 K, regardless of whether oxygen (O2) gas was introduced
during the deposition process.
The photocatalytic activity of the deposited TiO2 thin films was evaluated by
immersing the samples (size 2.5 cm2) in an aqueous methylene blue solution and
irradiating them with a black light lamp. The photo-induced hydrophilicity was
studied by contact angle measurements under UV irradiation. The highest
72 Chapter 2
Figure 2.20 Sketch of the VAPE set-up. (Reproduced with permission from ref. 138.)
photocatalytic activity and photo-induced hydrophilicity were obtained in

anatase TiO2 thin films prepared at 573 K. Moreover, a transparent and con-
ductive anatase TiO2 thin film with a resistivity of 2.6 101 O cm was prepared
at a substrate temperature of 673 K without the introduction of O2 gas.
2.4.2.2 Electron Beam Physical Vapor Deposition

In this technique the material to be deposited is heated to a high vapor pressure
by electron bombardment in high vacuum. Reference 139 reports the prepara-
tion of ca. 1.2-mm thick TiO2 films by electron-beam evaporation. Figure 2.21
shows a sketch of the set-up. The chamber was evacuated by a mechanical
pump, the distance between the electron-beam evaporation system and the
substrate holder was 550 mm, and deposition occurred in an O2 atmosphere
using rutile TiO2 as the source material. The temperature of the substrate was
maintained at 523 K by a quartz lamp. Various films consisting of mixtures of
amorphous or anatase TiO2 were prepared at various O2 pressures that influ-
enced both the crystallinity and the hydrophilicity (which was evaluated by
contact angle measurements).
2.4.2.3 Sputtering Deposition: Reactive Direct Current (DC)

and Radio Frequency (RF) Magnetron Sputtering
Sputtering consists in removing atomized material from a solid due to energetic
bombardment of its surface layers by ions or neutral particles.
Figure 2.21 Sketch of an electron-beam (E-beam) evaporation set-up. (Reproduced

with permission from ref. 139.)
Magnetron sputtering is a powerful and flexible vacuum (o106 atm)

coating process that can be used for a wide range of materials and is especially
suitable for large-scale film deposition, due to its low-cost and easy controll-
ability. An inert gas such as, for instance, argon is introduced to reach the
minimum value of pressure needed to operate the magnetrons, which are a class
of cold cathode discharge devices used generally in a diode mode. The differ-
ence between a magnetron cathode and a conventional diode cathode is the
presence of a magnetic field. A surface atom becomes sputtered if the energy
transferred is more than three times the surface binding energy (approximately
equal to the heat of sublimation). Sputtering of a target atom is just one of the
possible results of ion bombardment of a surface. The second important pro-
cess is the emission of secondary electrons from the target surface that enable
the discharge to be maintained. The target materials range from pure metals,
where a DC power supply can be used, to semiconductors and isolators, which
require a RF power supply or pulsed DC. A magnetic field is used to trap
secondary electrons close to the target; these electrons follow helical paths
around the magnetic field lines, increasing the number of the ionizing collisions
with neutral gas molecules. This phenomenon enhances the ionization of the
74 Chapter 2
Substrate
Coating - Electron
Electric Lines of force
field of magnetic field + Argon ion
- -
- Plasma Atom sputtered
-
from target
- - -
- - + -
+ +
- +
+ + + +
Target-cathode
Target-cathode
Cooling Cooling
Anode
Magnets
Figure 2.22 Typical RF sputtering working scheme.
plasma near the target, producing a higher sputter rate. The sputtered atoms
are not charged and are not affected by the magnetic field.
The set-up used for RF magnetron sputtering is sketched in Figure 2.22.
Among various types of films, TiO2 films have been prepared by this tech-
nique.140–148
Reference 140 reports the preparation of TiO2 films starting from a Ti metal
target and their photocatalytic behavior, although films prepared by spray
pyrolysis are sometimes reported to be more photoactive.136 The films were
deposited on an unheated non-alkali glass (AN, Asahi Glass) by RF reactive
magnetron sputtering. Depositions were carried out under various RF sub-
strate biases and the total gas pressure during deposition was 1.0 or 3.0 Pa. The
oxygen flow ratio [O2/(O2 þ Ar)] and RF sputtering power were kept constant
at 60% and 200 W, respectively. The photocatalytic decomposition of acet-
aldehyde under UV illumination was carried out to test the samples.
Transmission electron microscopy has been used to study the structure,
morphology and orientation of thin TiO2 films prepared by reactive RF
magnetron sputtering on glass slides at different substrate temperatures (373–
673 K).143 The microstructure and photocatalytic reactivity of TiO2 films
depended on the deposition temperature. In the temperature range examined,
all film samples exhibited a porous nanostructure and the dimension of the
particles grew upon increasing the deposition temperature. Films were amor-
phous at 373 K, and anatase phase was found at T Z 473 K. A preferred
orientation was noticed for films deposited between 473 and 573 K, whereas
films obtained at 673 K showed a random orientation. The most photoactive
films to abate Rhodamine B present in waste water were those deposited at
523 K, due probably to the high degree of preferred orientation and to the
satisfactory crystallinity and nanoporosity of the anatase phase.
DC magnetron sputtering has been used to form transparent TiO2 thin films
(200–300 nm thick) on glass substrates.145 A semiconducting TiO2–x target in
pure Ar was used at pressures ranging between 0.1 and 1.0 Pa. Post-deposition
heat treatment carried out at different temperatures allowed achievement of the
crystallization of anatase TiO2. Both the as-deposited and heat-treated films
were subjected to UV–VIS, SEM and XRD investigation; it was found that the
pressure of argon during the deposition process influenced the structure
modification that occurred throughout the heat treatment. In addition,
decomposition of ethanol in synthetic air was used as a probe reaction to test
the photocatalytic activity, with the aim of relating it to the microstructures of
the samples.
The existence of a solid–solid interface in TiO2 films produced by the reactive
DC magnetron sputtering147 explained the high photoactivity of mixed phase
TiO2 catalysts. The sputter deposition allows easy control of the phase and
interface formation. Moreover, the influence of oxygen partial pressure, target
power, substrate bias, deposition incidence angle and post-annealing treatment
on the structural and functional characteristics of the catalysts has been stu-
died. The photocatalytic activity of the films for the photooxidation of acet-
aldehyde under UV illumination in the gas phase was higher (normalized for
surface area) than that showed by mixed phase TiO2 samples prepared by other
methods (flame hydrolysis powders and sol-gel deposited TiO2 films), although
the comparison between films prepared by means of very different techniques or
between films and powders is difficult, due to the many variables that could
influence the photoactivity to differing extents.
TiO2 thin films have been deposited very recently on three different unheated
substrates by DC magnetron sputtering.148 The effects of sputtering current
and deposition time on the crystallization of TiO2 thin films were studied. The
TiO2 thin films were deposited at three sputtering currents, 0.50, 0.75 and 1.00
A, with deposition times of 25, 35 and 45 min, respectively. Anatase films were
obtained at low sputtering current values and under all deposition conditions.
The crystallinity of the anatase phase with grain size in the range 10–30 nm
increased as the sputtering current and deposition time increased.
2.4.2.4 Cathode Arc (Plasma) Deposition

In this case a high power arc directed at the target material blasts away some
material into a vapor sputter. Detailed information on cathode arcs can be
found in ref. 149.
In direct cathode arc deposition, a flow of a highly ionized metal plasma from
a cathode arc spot transfers coating material to the substrate surface. A dis-
advantage of this method is the formation of droplets (also called macro-
particles) in the cathode arc flow that could negatively influence the critical
properties of the coatings. Figure 2.23 shows a sketch of cathode arc deposition.
76 Chapter 2
Droplets
Cathode
arc spot
Arc plasma
Cathode expansion zone
Cathode
voltage zone
Negatively biased
Anode substrate to be
coated
Figure 2.23 Sketch of cathode arc deposition process.
Few applications of this technique can be found for the preparation of TiO2
thin films, although one report150 deals with the obtainment of TiO2 films on
glass substrates at various temperatures (from room temperature to 673 K)
using an unfiltered cathode arc device. The films deposited at temperatures
lower than 573 K were amorphous, whereas those obtained at higher tem-
peratures grew as a crystalline anatase phase. The phase transition amorphous-
to-anatase was observed after post-annealing at 673 K. The average transmit-
tance was always higher than 80% and it was slightly higher for films obtained
at the highest temperatures. The size of the grains of the as-deposited crystalline
films was ca. 20 nm and the surface roughness ca. 2 nm.
2.4.2.5 Pulsed Laser Deposition (PLD)

The use of this technique allows production of multicomponent materials.
Ablation of the target occurs by means of a high-power laser and deposition of
the vapor phase onto the substrate affords stoichiometric layers that match the
target material.
The PLD technique, although industrial uses are known, is generally
recognized as a well-established laboratory coating technology, because
industrial usage is restricted mainly by the need for large-area deposition. The
combination of PLD with other techniques such as magnetron sputtering has
been suggested with the aim of potential industrial application.151
Figure 2.24 shows a schematic of a typical PLD system.
Some TiO2 films prepared by PLD have been reported, as for instance in refs
152–156, although photoactivity tests appear only rarely.156
A colloidal TiO2 nanoparticle film has been deposited on a quartz substrate
and the morphological and optical properties determined.153 Atomic force
microscopy demonstrated that a good uniformity of deposition was obtained.
Port with
quartz window Laser beam
Heatable
substrate stage
Substrate
Target
Vacuum chamber
Figure 2.24 Scheme of pulsed laser deposition.
Agglomerates with dimensions of ca. 1 mm in size were observed. The optical

constants, the energy gap and the film thickness were determined by UV–Vis
transmission spectra, recorded in the 200–800 nm range. The optical constants
obtained agree with values reported in literature for TiO2 nanoparticle thin
films.
Reference 154 reports the growth of TiO2 nanocrystalline films on Si sub-
strates by PLD. Rutile sintered targets were used and were irradiated by a KrF
excimer laser (l ¼ 248 nm, pulse duration B30 ns) in a controlled oxygen
environment at a constant substrate temperature of 923 K. The structural and
morphological properties of the films were studied by varying the oxygen
partial pressure (0.05–5 Pa) and the laser fluence (2–4 J cm2). Both rutile and
anatase phases formed, but the latter disappeared at the highest laser fluences.
X-Ray photoelectron spectroscopy (XPS) measurements allowed the determi-
nation of the stoichiometry of the grown films. The surface morphology of the
deposits, studied by scanning electron (SEM) and atomic force (AFM)
microscopies, indicated that they were nanostructured films. The dimensions
and density of the nanoparticles observed at the surface depended on the partial
pressure of oxygen during growth. The smallest particles (ca. 40 nm diameter)
were obtained at the highest pressures of inlet gas.
The photocatalytic properties of different crystalline titanium dioxide films
have been evaluated and compared.156 The films grew directly on titanium
substrates by surface anodization (see anodic oxidation in the following) and by
PLD on titanium and silicon substrates, followed by thermal annealing. Not
only were the structure and morphology of the films studied by means of SEM
observations and X-ray diffraction analyses, but also photocatalytic tests on
stearic acid mineralization were performed. The results indicated higher
78 Chapter 2
photocatalytic efficiency for PLD layers. This finding can be explained by
considering the different microstructured/microporous morphology of the
surfaces. Notably, moreover, PLD TiO2 films with a relatively high content of
rutile phase showed lower photocatalytic efficiency than films containing
mainly the anatase phase.
2.4.3 Chemical Vapor Deposition (CVD)

Chemical vapor deposition (CVD) is a chemical process used to produce high-
purity solid materials with high performance. The process is often used in the
semiconductor industry to produce thin films. In a typical CVD process, one or
more volatile precursors react and/or decompose on the surface of a substrate
where the desired film is formed. The volatile by-products can be removed by
means of a gas flow.
Chemical vapor synthesis (CVS) is a modified CVD method where the
parameters of the process are adjusted to produce nanoparticles instead of
films. Chemical vapor condensation (CVC), chemical vapor reaction (CVR)
and chemical vapor precipitation (CVP) are synonyms used frequently in the
literature. Some precursors both in CVD and CVS are hydrides, carbonyls,
metallorganics, chlorides and other volatile compounds in gaseous, liquid or
solid state. A limitation of the CVS process is the difficulty in finding suitable
precursors. The energy necessary to convert the reactants into nanoparticles is
supplied by means of flame, hot wall, plasma, and laser reactors. Important
parameters to be controlled to obtain good reproducibility are the total pres-
sure, partial pressure of the precursor, carrier gas, temperature or power of the
energy source, and reactor geometry. Modifications of the precursor delivery
system and the reaction zone allow the synthesis of pure and doped oxides,
coated and functionalized nanoparticles, and granular films. Figure 2.25 gives a
schematic representation of physical vapor deposition, chemical vapor
deposition and chemical vapor synthesis.
TiO2 films have been prepared by CVD.157–164 In some cases the photo-
catalytic activity of the films was tested.
The synthesis of anatase TiO2 supported on porous solids by coating anatase
TiO2 onto three different particle supports, i.e., activated carbon, g-Al2O3 and
silica gel, was studied in ref. 158. The presence of H2O (vapor) during or before
the CVD process was found essential to obtain anatase TiO2 on the surface of
supports. High inflow concentration of the precursor (titanium tetraisoprop-
oxide), high CVD reactor temperature and long coating time gave rise to
blockage problems, due to deposition of particles that occurred together with
the vapor deposition. Macroporous silica gel with a high density of surface
hydroxyl groups and high surface area was found to be the best support and
TiO2/SiO2 samples showed the highest activity in the photodegradation of
phenol in water.
The selective deposition of TiO2 films starting from titanium isopropoxide as
the precursor was performed by using a KrF laser CVD technique on a quartz
Figure 2.25 Schematic representation of physical vapor deposition (PVD), chemical

vapor deposition (CVD) and chemical vapor synthesis (CVS) of nano-
crystalline powders (to form a film on a collecting surface). (Courtesy of
http://python.rice.edu/Barb/Courses/Images/360_02_handout9.jpg
http://www.uni-due.de/ivg/nano/synthesis_nppt.shtml.)
substrate under the fixed laser fluence of 450 J m2.159 The substrate tempera-
tures, laser repetition rates and supply rates of the precursor ranged between
328 and 573 K, 10 and 100 Hz, 60 and 300 mg h1, respectively. Rutile and/or
anatase phases were found in the film for all experimental conditions used. Low
substrate temperature, low laser repetition rate and high supply rate of the
precursor are beneficial for rutile formation.
TiO2 photocatalytic films prepared by low-pressure metal–organic (LPMO)
CVD, by using titanium tetraisopropoxide as the precursor and various reac-
tion temperatures and deposition times, have been characterized.162 The results
indicated that the film thickness was linearly proportional to the deposition
time, while their structure depended not only on the deposition time but also on
the reaction temperature. Moreover, the photocatalytic decomposition of
methylene blue in aqueous solution was chosen as probe reaction to test the
photoactivities of the films. The anatase and rutile TiO2 films showed the
80 Chapter 2
highest photocatalytic activity, whereas the amorphous TiO2 films showed
lower activities. The photocatalytic activity depended on film thickness non-
linearly and the optimum thickness is located between 3 and 5 mm.
Pure brookite phase TiO2 crystals with high specific surface area have been
deposited at room temperature on silicon(100) substrates by means of plasma-
enhanced chemical vapor deposition. Titanium tetraisopropoxide in the vapor
phase and argon–oxygen mixtures, under an applied substrate DC bias voltage
of –250 V, were used.163 X-Ray diffraction analysis for the as-deposited TiO2
confirmed the presence of a crystalline brookite phase.
Thin TiO2 films have been deposited using a RF plasma-enhanced chemical
vapor deposition.164 The optical properties and thickness, determined by means
of UV–Vis absorption spectrophotometry, indicated a good optical quality and
their potential application both as interference optical filters and photocatalytic
surfaces. The structural analysis, carried out by Raman shift spectroscopy,
showed that the coatings posses an amorphous structure. However, Raman
spectra of the same films subjected to thermal annealing at 723 K revealed the
appearance of the anatase crystalline form. Surface morphology of the films
was also investigated by atomic force microscopy, which indicated the presence
of granular, broccoli-like topography.
2.4.4 Chemical Bath Deposition

The chemical bath deposition (CBD) technique is the cheapest known techni-
que for the preparation of films of various compounds (oxides, sulfides, etc.). It
is based on direct deposition onto the chosen support of a compound produced
from precursor species by means of chemical reaction(s). It is essential to check
the temperature, pH and experimental conditions under which the compound
of interest must be produced before its deposition. The films could be subjected
to a heating treatment as a second step.
Figure 2.26 shows a CBD set-up.
Some papers report the preparation of TiO2 films by this method165,166 but,
notably, the adhesion of TiO2 to the support is not satisfactory in most cases,
particularly for films intended to be used in photocatalytic reactions. Conse-
quently, not many relevant papers can be found in the literature.
TiO2 films on glass substrates have been prepared at room temperature by
this method starting from an aqueous peroxotitanate solution.165 The films
were 117 nm thick and consisted of closely packed particles (10–15 nm in dia-
meter) aggregated into large grains (50–100 nm). Anatase TiO2 thin films were
obtained by heating the as-deposited thin films at 773 K for 1 h in air.
Dense, transparent rutile TiO2 films 2.5 mm thick have been obtained on a F-
doped SnO2-covered glass substrate.166 The starting solution contained per-
oxotitanate complex ions, which were relatively stable under the experimental
conditions chosen. Kinetic studies suggested that the precipitation started from
the formation of amorphous solids, followed by crystallization through a dis-
solution–recrystallization process. Anatase was detected only for powders
pH
Temperature probe
probe Substrate holder
Substrate
Magnetic bar
Hot plate
Figure 2.26 Chemical bath deposition set-up.
collected from solutions after film preparation, not for films, and the trans-
formation from amorphous into anatase was hypothesized to occur before
further transformation of anatase into rutile.
2.4.5 Thermal Oxidation and Anodic Oxidation

Thermal oxidation is one way to produce a thin layer of oxide on the surface of
a wafer. The technique forces an oxidizing agent, which could be water vapor
(wet oxidation) or molecular oxygen (dry oxidation), to diffuse into the wafer at
high temperature and react with it. Thermal oxidation of silicon, for instance, is
usually performed at between 1073 and 1473 K, resulting in the so-called high-
temperature oxide (HTO) layer. Wet oxidation, generally, is preferred to dry
oxidation for growing thick oxides, because of the higher growth rate.167
Thermal oxidation has been sometimes applied to metallic titanium to form
a film of TiO2 on the metallic surface that can then be used to carry out
photochemical water splitting or can work as anode in an electrochemical
photocell where hydrogen is produced.168,169
Reference 168 describes the preparation of chemically modified n-type TiO2
by controlled combustion of Ti metal in a natural gas flame. This material, in
which carbon substituted some lattice oxygen atoms, absorbs light at wave-
lengths below 535 nm and has a lower band-gap energy than rutile (2.32 instead
of 3.00 eV). By applying a potential of 0.3 V, water splitting occurred with a
total conversion efficiency of 11% and a maximum photoconversion efficiency
of 8.35% (illumination equal to 40 mW cm2).
82 Chapter 2
+ Anode - Cathode
(substrate)
Power
supply
Diluted H2SO
2SO
4 4
Figure 2.27 Set-up for anodic oxidation.
The anodic oxidation method allows the generation of an oxide film having
protective, decorative or functional properties on a surface of the corre-
sponding metal.170
This technique has been used to prepare TiO2 films in a diluted H2SO4
solution, and the parameters of their formation have been studied in depth.171
The set-up of this technique (Figure 2.27), which can be used quite easily,
consists of a power generator, an electrolyte, titanium samples that are con-
nected to the positive pole (anode) where oxidation takes place, and another
metal (generally titanium) working as cathode connected to the negative pole of
the generator, where reduction reactions take place.
The electrochemically enhanced oxidation of a metal under some circum-
stances yields solid oxide nanotubes. Anodic oxidation of Ti in electrolytes
containing a small amount of fluoride has been used to convert Ti into TiO2
nanotubes.172 Ordered nanotube arrays have been obtained by anodization of
titanium in fluoride-based baths.173,174 The nanotubes showed various pore
sizes (22–110 nm), lengths (200–6000 nm) and wall thicknesses (7–34 nm).
Nanotubes with different shape (cylindrical, tapered), length and wall thickness
have been produced by varying the anodization parameters such as electrolyte
concentration, pH, voltage and bath temperature. They are of great interest for
use in water photoelectrolysis, photocatalysis, heterojunction solar cells and gas
sensing.
Very recently nitrogen-doped TiO2 films with amorphous nanotubular
morphology and enhanced specific surface area were produced, inducing the
growth of the oxide layer directly on titanium substrates.175 Anodization was
performed in fluoride-containing electrolytes and the doping was achieved by
means of thermal treatments in a nitrogen atmosphere. The anodically formed
N-doped TiO2 layers showed high efficiency in the photodecomposition of
Rhodamine B under visible radiation.
2.4.6 Electrophoretic Deposition
In the electrophoretic deposition process (EDP) colloidal charged particles
suspended in a liquid are forced by a direct current (DC) electric field to move
toward an oppositely charged electrode, onto which they are deposited.176 This
low-cost method not only allows us to easily control the thickness of the
coatings, but also to coat surfaces of conductive substrates with large areas.
EDP has been applied very frequently to produce ceramic layers from powders
dispersions.177–179 Figure 2.28 shows a sketch of the EDP set-up, which consists
of an electrochemical cell.
TiO2 coatings have been produced on glasses,180 stainless steel,181,182 SiC and
carbon fiber.183
The TiO2 coatings were produced on glass foam substrates by EDP and sol-
gel method with the aim of imparting to the surface antibacterial and photo-
catalytic properties.180 Charged TiO2 nanometric particles TiO2 suspended in
acetylacetone were used to obtain coatings on the glass foam substrates. Best
results were obtained by applying 25 V for 4 min and a subsequent thermal
treatment (723 K for 1 h). In addition, multilayer sol-gel TiO2 coatings on glass
foam were also prepared, which were subjected to the same thermal treatment.
Both techniques led to partially microcracked coatings that were, however, well
adhered to the glass foam substrate.
TiO2 films produced on various substrates have been tested for photo-
catalytic degradation of malic acid (hydroxybutanedioic).181 Two TiO2 samples
supported on stainless steel by EPD showed a lower catalytic activity than
those supported on quartz by a dip-coating procedure. The results were
explained by considering the negative role played by some cationic impurities
(Si41, Na1, Cr31 and Fe31) that were present in the TiO2 layer as a
DC
DC
- +
Cathode Particle Anode
+ +
+ + +
+ + +
+ + +
+ +
+ +
+ + + +
+ +
+ + +
+ + +
+ + +
+ + +
+
+ +
+
+
Figure 2.28 Schematic of electrophoretic deposition process set-up.

84 Chapter 2
consequence of the thermal treatment necessary to improve the cohesion and
adhesion to the support. TiO2 Degussa P25 suspended in acetone (1 g in 100 ml)
was used to coat the stainless steel foils. The suspension was first homogenized
by sonication and stirred magnetically during the deposition. A counter-elec-
trode of Pt acting as the cathode was placed in the suspension just in front of
the stainless steel substrate with the same size and shape. The applied potential
between the two electrodes was either 125 V (for 4 min) or 200 V (for 2 min),
depending on the sample. TiO2 particles, due to their natural surface charge,
moved to the stainless foils, forming a layer. Subsequently, the two samples
were heated in a N2 flow at 973 K for 4 or 8 h.
Crack-free rough anatase TiO2 coatings have also been prepared on stainless
mesh by an EDP technique, and they were found active for the photocatalytic
oxidation of 2-propanol to acetone.182
Finally, ref. 184 describes the preparation of an electrophoretically deposited
film – without the use of a surfactant or any post-thermal treatments – that is
potentially useful for application in flexible dye-sensitized solar cells. The
resultant film was composed of wide band gap nanocrystalline TiO2.
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CHAPTER 3
Unique Properties of Supported

TiO2
3.1 Superhydrophilic versus Photocatalytic Character
This chapter will introduce the reader to the most relevant properties of dif-
ferent materials where TiO2 is supported in the shape of a thin film (for
instance, glass) or of a blend exteriorly deposited (such as in concrete and
paving blocks). Details about commercial, prototypes and promising products
are given in subsequent chapters.
The most popular property of TiO2-based materials is undoubtedly the
ability to degrade pollutants in air and water, affording a cleaning effect for
both air or water and the material that TiO2 is deposited on. This behavior is
the result of the semiconducting properties of TiO2, which, when irradiated
with appropriate light, can give rise to redox reactions, as widely discussed in
Chapter 1 and in the literature.1 Applications related to this property are
widespread, both in open and in enclosed areas. Thus, indoor car parks have
been equipped to test the de-polluting efficiency of a TiO2-containing paint in
an indoor polluted environment; 917 m3 of enclosed area were monitored by
gas chromatography to measure all the gaseous pollutants (NOx, SO2, CO) and
CO2, and, in addition, the roof (322 m2) was covered with an acrylic paint
treated with 10% TiO2 prepared by Millennium Chemicals.2 The results, taking
into account the reduction of pollution due to car emission variation, showed
that the photocatalytic removal of NOx was about 20%, with a photocatalytic
rate of the order of 0.1 mg m2 s1. This study demonstrated that TiO2-modified
materials can work properly even in an enclosed, heavily polluted environment.
Beside the photocatalytic effect, we can regard superhydrophilicity as the
other primary characteristic of TiO2-based materials. This effect was discovered
accidentally during experiments carried out at the laboratories of Toto, Inc., in
1995.
When water drops are deposited on a TiO2-functionalized surface, they show
a contact angle of several tens of degrees. Upon irradiation by UV-light (even
the small fraction present in solar light) water begins to exhibit a decrease in

98
Unique Properties of Supported TiO2 99
contact angle, and starts to spread out flat instead of beading up. After a certain
time the water contact angle reaches ca. 01, meaning that the surface became
superhydrophilic, i.e., totally non-water-repellent.3 If the material is then kept
in the dark, a very low contact angle is retained for a certain time. When the
surface is composed of TiO2 coupled to SiO2 or Si-containing compounds with
siloxane bonding the retention of superhydrophilic behavior in the dark is very
high and can last several days. After a given time, however, the angle starts
increasing and the surface becomes hydrophobic again. Simple exposure at
UV-light, though, can impart again the hydrophilic properties to the surface.
This property is permanent and is retained provided that the film is well sup-
ported and does not peel off.
Figure 3.1 shows schematically the steps yielding a superhydrophilic surface:
upon light irradiation, –OH surface groups are produced with high affinity for
water, so that H2O molecules can occupy a thin layer of space, constituting a
uniform sheet rather than forming single drops.
In terms of the chemical mechanism, electrons tend to reduce Ti(IV) cations
to the Ti(III) state, and the holes oxidize the O2 anions. In the process, oxygen
atoms are ejected, creating oxygen vacancies.4 This process can coexist with the
photocatalytic effect, generated by electrons, giving rise to redox reactions
involving the target pollutants rather than Ti cations. Depending on the film
morphology one phenomenon can prevail over the other. Figure 3.2 shows this
mechanism; clearly the hydrophilic behavior depends on the vacancies finally
occupied by H2O molecules. As far as water molecules are concerned, when the
TiO2 surface is irradiated with UV light under ambient conditions, the dis-
tribution of hydrogen bonds in the H2O molecules decreases, along with the
surface tension of H2O clusters. Furthermore, the decrease in the amount of
H2O adsorbed on the TiO2 surface implies a decrease in the outer surface areas
of the H2O clusters. It can be thus stated that the surface relaxation energies of
Figure 3.1 Physicochemical principles of light-induced superhydrophilicity. (Repro-

duced with permission from ref. 3b.)
100 Chapter 3
Figure 3.2 Mechanism of light-induced superhydrophilicity. (Reproduced with per-

mission from ref. 4.)
Figure 3.3 Schematic diagrams of shapes of H2O clusters on TiO2 surfaces: (a) before
and (b) after UV light irradiation. (Adapted with permission from ref. 3a.)
the H2O clusters are stabilized and the surface areas of the H2O clusters
increase spontaneously. A strict consequence of this behavior is the lower
amount of adsorbed H2O molecules, driven by a force behind the H2O clusters
spreading out, thermodynamically, on the TiO2 surfaces (Figure 3.3).
The indicated reactions are, notably, completely reversible. Interestingly, the
hydrophilicity of a TiO2 surface hampers the adhesion of fatty compounds, making
such surfaces very easy to clean, which is highly desirable for example in kitchens.
Figure 3.4 Dependence of photo-induced change in water contact angle of TiO2/SiO2

composite films after (a) exposure to air for 2 weeks; (b) UV irradiation.
Surfaces can have more photocatalytic character and less superhydrophilic

character, or vice versa, depending upon the composition and the manu-
facturing process. The presence of SiO2 greatly enhances the hydrophilic
properties of TiO2 films and in particular allows for long-lasting super-
hydrophilic behavior even after many days in a dark state.5 Increasing the SiO2
amount up to 40% yields an improvement in hydrophilicity (Figure 3.4).
Interestingly, the self-cleaning effect has an analogous trend. This synergetic
effect can be explained as follows: numerous –OH groups can be adsorbed on
the surface due to hydrophilicity, hence the photocatalytic activity is enhanced
due to easier formation of HOd radicals. Conversely, the film surface can
adsorb organic pollutants, which tends to turn the hydrophilic surface into a
hydrophobic one. Photocatalysis, however, can decompose the organic com-
pounds on the surface, yielding again a high hydrophilicity. This is how the
photocatalytic activity helps in preserving the film hydrophilicity.
The improved performances of SiO2/TiO2 binary systems are attributed to
the silicon cation, which is still bonded to the same number of oxygen atoms
even though the oxygen atoms now have a new coordination; this creates a
charge imbalance. Thus, Lewis sites are expected to form due to the positive
charge in a TiO2/SiO2 binary metal oxide, thereby improving both adsorption
of water and photocatalytic reactivity.
Hydrophilicity plays a very important role in maintaining the self-cleaning
characteristic of a surface. The vulnerability of an exterior surface to soiling is
strictly related to its contact angle with water. For instance, plastic materials,
such as fluorocarbons, are more likely to be soiled than sheet glass or tiles. Thus
a superhydrophilic material showing a water contact angle of 01 can be very
102 Chapter 3
improbably smeared. Nevertheless, a surface that is only superhydrophilic
cannot always guarantee a self-cleaning effect. The photocatalytic effect indeed
plays an important role in decomposing the soiled compounds and organic
compounds to acquire a self-cleaning effect directly, and in decomposing the
soiled compounds to recover the hydrophilicity to acquire self-cleaning char-
acter indirectly.
The hydrophilic feature plays a primary role in avoiding the undesirable
fogging effects typically present in indoor windows, car glass, etc. For instance,
a TiO2 coating hampers the water condensation and formation of ice crystals
that produce an opaque layer that reduces the transparency of glass or the
visibility of traffic mirrors.6 This point is detailed in Chapters 4–6.
Multicomponent films have been developed to impart particular properties
to the resulting coating or to protect the underlying substrate. For instance, a
multilayer structure consisting of a polyurethane (PU) protective layer on a
substrate covered by two layers of photocatalytic TiO2 and, finally, by
immobilized TiO2 particles (deposited from a suspension containing PU as
binder) has been used with substrates such as high-density polyethylene
(HDPE), poly(vinyl chloride) and borosilicate glass (BK7).7 The fabricated
coatings finally underwent an etching treatment by reactive oxygen-plasma,
thus exhibiting a photocatalytic activity in the degradation of palmitic acid.
Oxygen-plasma treatment indeed produces hydrophilic groups (such as non-
stoichiometric TiOx) on the surface of TiO2. Moreover, this treatment can add
polar groups, such as hydroxyl groups, to the PU surface. Thus the PU binder
between TiO2 particles can actively contribute to the superhydrophilic effect,
once the oxygen-plasma treatment has been performed.
Figure 3.5 shows a sketch of some contact angles for different multilayer
films deposited on HDPE substrates. Case B refers to a film with PU binding,
thus resulting in a more hydrophobic surface than case A, due to the presence
of the organic component. It can be seen that superhydrophilicity is not present
unless the oxygen-plasma treatment is performed (case C). The addition of
palmitic acid on the film (case D) followed by UV irradiation causes super-
hydrophilic behavior and photocatalytic degradation of the pollutant, even-
tually yielding a 01 contact angle (case E).
3.2 Antireflection
Composite films containing TiO2 are used to obtain antireflective surfaces. In
particular, some excellent results have been obtained by coupling TiO2 and
silica. This property is almost exclusively used in glass or silicon wafer coatings.
In the former case the coatings allow for a clear view through the glazing by
increasing the light transmittance and avoiding negative effects on visual
observation like double image, reflection of light sources, etc.8 The basis of the
antireflective behavior of TiO2-based glass-coatings is widely discussed in
Chapter 4. Here we report instead the recent application developed by the
German company HEGE Solar, working in the field of photovoltaics.
Figure 3.5 Water contact angles on HDPE samples at different stages of fabrication.
The basic sample consisted of a substrate (HDPE), a protective PU
coating, and two layers of TiO2. The images show a sample (A) without a
PU binder, (B) with a PU binder, (C) after a 15 s plasma treatment and 3 h
UV illumination, (D) after the addition of palmitic acid to the surface and
(E) after 24 h UV illumination of the coating with palmitic acid.
Researchers at this company have realized a new antireflective coating (TOP-

NANO-HEGEs Coating) that boosts the efficiency of solar panels and allows
sunlight to be absorbed from a very wide range of angles.9
Notably, a standard silicon solar cell absorbs just 2/3 the sunlight it receives.
By covering the module with the described nanoengineered coating this value
rises to more than 95%. Moreover, gains in absorption are consistent across the
entire spectrum of sunlight, from ultraviolet to infrared and the absorption
even takes place with very low solar rays angles (at dawn and sunset).
The coating is based on seven tiny layers, with a single thickness of 50–
100 nm. They are basically made of TiO2 tilted nanorods and silica and can be
easily deposited (Figure 3.6).
This series of layers also helps to bend the flow of photons so that they can
thus reach the silicon wafers and be absorbed rather than reflected off.
As illustrated in Chapter 2, sol-gel techniques are probably the most used
ones to obtain precursors to be deposited in the form of a thin film of ca.
100 nm. Thus antireflective coatings can be obtained on silicon substrates by
applying a TiO2 sol synthesized through the hydrolysis and polycondensation
of a titanium alkoxide (such as titanium tetrabutoxide) with water in anhydrous
ethanol such as the solvent.10
Figure 3.7 shows the reflectance spectra of the uncoated and coated silicon
substrates. The thicknesses of the films were adjusted to give a minimum in
reflectance at l ¼ 600 nm. However, the reflectance of coated samples is lower
for all wavelengths; in particular, a strong decrease from 37% to 1.5% is seen at
600 nm. Owing to a small difference in thickness, samples 2 and 3 show a certain
104 Chapter 3
Figure 3.6 A worker at HEGE Solar applying a nanocoating based on TiO2 nanor-
ods and silica on a monocrystalline solar module. (Photograph courtesy of
HEGE Solar.)
Figure 3.7 Hemispherical reflectance spectra of uncoated silicon (1) and silicon
coated with TiO2 films (2, 3). Curves 2 and 3 refer to sol-gel solutions
prepared with different alkoxide/ethanol ratios and dip-coated at different
withdrawal rates. (Reproduced with permission from ref. 10.)
shift in wavelength minimum, whereas the shift of the reflectance minimum
intensity is determined by the difference in refraction indices.
By calculating the solar averaged reflectance data at the AM1.5 solar photon
spectral distribution,11 it is possible to integrate the values ranging from
wavelengths of 320 to 1120 nm. For uncoated silicon a value of 0.387 was
obtained while 0.120–0.132 was found for TiO2-coated silicon, showing a sig-
nificant improvement in antireflective properties.
3.3 Photoprotection and Anticorrosive Effects

The developed TiO2 sols (i.e. nanoparticles finely dispersed in an aqueous or
organic solvent) applicable by means of an easy coating system, such as dip-
coating, spray-coating or through a brush, have in some cases become com-
mercialized. TiPEt for instance is a leading Chinese company in the produc-
tion of photocatalysts. They use advanced nano-hydrosynthetic technology
that has resulted in the constitution of a product line that includes eight series
products and more than 30 kinds of different photocatalyst products in these
series.12 They present photocatalyst coating products as suitable devices for
high-efficiency and professional application, adding that the line represents the
most important one in TiPE series. The possible fields of application cover the
environment, healthcare, chemicals, buildings and energy fields. This company
provides also Pt-doped TiO2 sols to improve activity under visible light
irradiation.
Beside the role of degrading pollutants, with an important effect in deo-
dorizing the environment by destroying the malodorous species present in air, a
superhydrophilic behavior that avoids drops and fog formation on glass
favoring its self-cleaning, thus also hampering the deposition of smog on
outdoor architectural concrete elements, these kind of coatings can also work
as protective layers against UV-irradiation for various materials.
Poly(ethylene terephthalate) (PET) can for instance be effectively photo-
protected thus preventing its photo-aging.13 It is possible indeed to cover the
surface of the polymer film by implementing a thin bilayer Al2O3/TiO2 ceramic
coating. TiO2 coating absorbs the UV radiation that could damage the polymer
whereas Al2O3 provides a barrier against oxygen diffusion.
The films were deposited by means of a sputtering system equipped with an
RF generator with bulk Ti and Al2O3 targets. They were tested in the photo-
degradation of Rhodamine B in aqueous solution.
Since PET is a polymer degradable by irradiation at lo330 nm, natural
solar light produces stable changes in its structure. Depositing a film of Al2O3
does not change the absorption spectra of PET, whereas a TiO2 layer properly
plays this role. The photodegradation of PET produces hydroxylated species
such as alcohols, acids and hydroperoxides that can be monitored by IR
spectroscopy, at 3470 cm1.
Figure 3.8 shows the change in the absorbance at 3470 cm–1 versus irradia-
tion time for PET, Al2O3- and TiO2-coated PET, and PET coated with Al2O3/
106 Chapter 3
Figure 3.8 Change in absorbance, at 3470 cm1, determined from IR spectra, versus
irradiation time. PET: uncoated PET; A100: PET coated by a 100–nm
thick Al2O3 film; T500, T1200: PET coated by a 500– and 1200-nm thick
TiO2 film, respectively; S1-S4: different samples corresponding to TiO2/
Al2O3 coatings. (Reproduced with permission from ref. 13.)
TiO2 bilayers. The effectiveness of these layers in protecting the PET film from
photooxidation is quite evident. While the Al2O3-coated PET shows limited
improvement over uncoated PET, the TiO2-coatings exhibit some protection to
PET photodegradation. However, the effectiveness of these single coatings was
limited with respect to the double-layer coatings.
TiO2 films can yield significant protection against corrosion for metals such
as stainless steel.14 A two-step treatment can be applied to this material. First, a
conversion coating has to be realized, which is obtained by chemical oxidation
of the stainless steel substrate in an acidic solution containing additives such as
thiosulfate and propargyl alcohol to control the growth of the coating and to
obtain a high surface area. Second, a supporting TiO2 layer is formed by the
hydrolysis of titanium(IV) butoxide. A final calcination at 400 1C is required to
guarantee good adhesion and a transition from amorphous to anatase phase.
Corrosion tests of such materials have been performed as follows: in a closed
chamber a salt solution (3% NaCl, pH 6.8) is sprayed by means of a nozzle at a
controlled temperature of 35 1C. The manifestation of the first traces of cor-
rosion or red rust was monitored and the weight was measured at time intervals
to quantify the progress of the corrosion process.
Table 3.1 shows the weight measurements carried out during the corrosion
tests. Clearly, the protection against corrosion provided by the conversion layer
combined with TiO2 coating on stainless steel is very good. Accordingly, the
adhesion of such films was also very good.
Table 3.1 Mass variation measured during corrosion tests performed on
stainless steel untreated, treated with a conversion layer and trea-
ted with a conversion layer subsequently covered by a TiO2 film
(double coating).14
Steel t ¼ 168 h t ¼ 500 h
Bare steel þ 1.5 g þ 5.0 g
With conversion layer þ 0.83 g No measurement (too high)
With double coating –0.01 g –0.03 g
3.4 Bactericidal Properties

Upon UV-light irradiation titanium dioxide exhibits a powerful oxidizing effect
(fully described in its physicochemical aspect in Chapter 1) that can lead to a
proficient destruction of bacteria, viruses and moulds.15 Since the reaction
proceeds through a heterogeneous catalytic reaction, physical contact between
the target organism and the catalyst is necessary. This quite obvious fact is
indeed important because if our catalyst is supported on a material, such as a
ceramic tile, and the target organism is in the surrounding air the reaction
occurs only if the ceramic tile works as a highly-adsorbent device. Notably,
however, photocatalytic reactions are quite slow so that in the presence of a
high concentration of organisms the cleaning effect could be negligible.
The bactericidal effect is relevant since bacteria and viruses commonly pre-
sent in bathrooms, kitchens and hospitals can grow at an exponential rate
unless a tool such as TiO2 continuously lowers such growth.
The mechanisms of death of Escherichia coli cells have been particularly well
studied in homogenous media, since E. coli is one of the most common
pathogenic organisms. The mechanisms are, however, analogous to those
occurring on supported TiO2, such as in the photocatalytic tiles described in
Chapter 5. When irradiation of TiO2 occurs in direct contact with microbes, the
microbial surface is the primary target of the initial oxidative attack. Poly-
unsaturated phospholipids are an integral component of the bacterial cell
membrane, and they are very susceptible to be attacked by reactive oxygen
species, such as those produced upon irradiation of TiO2.
Several functions, namely, semipermeability, respiration and oxidative
phosphorylation reactions, rely on an intact membrane structure. When lipid
peroxidation occurs, thus, all forms of life are negatively affected.16
An estimation of membrane damage can be made by monitoring the
production of malondialdehyde (MDA), a product of lipid peroxidation.
Figure 3.9 shows the results of some experimental studies carried out by
incubating Escherichia coli cells in suspension with TiO2 (Degussa P25) and
irradiating the suspension with UV light (8 W m2) for 30 min with continuous
stirring. As shown, light and TiO2 slightly promote the cell destruction, whereas
the coupled presence of light and TiO2 significantly increases cell destruction.
Along with the cell membrane destruction, TiO2 also influences cellular
respiratory activities. The essential components of the respiratory chain are
108 Chapter 3
2.5
Dark
Light
MDA [mmol·mg cell dry wt-1]
2
Dark+TiO2
Light+TiO2
1.5
0.5
0
Dark Light Dark+TiO2 Light+TiO2
Figure 3.9 Effects of light and TiO2 on lipid peroxidation of Escherichia coli. MDA
stands for malondialdehyde, which is the main product generated during
lipid peroxidation.
contained in the membrane and damage to them produces irreversible effects on

respiration. Cell respiration can be determined by monitoring oxygen uptake in
the presence of an electron donor.
Generally, alterations in membrane architecture lead to conformational
changes in many membrane-bound proteins and electron mediators and to
changes in their orientation across the cell membrane. Functional changes of
membrane are thus produced.
Similar studies exhibited analogous results in the case of TiO2 supported in
the form of a thin film on a glass substrate.17
Interestingly, the survival change of Escherichia coli intact cells significantly
differs from that of spheroplasts, i.e., a modified cell lacking the peptidoglycan
layer and part of the outer membrane of the cell envelope. Figure 3.10 shows
that spheroplasts exhibit a simple single-exponential decay dynamics, with a
higher rate constant than that for the intact cells under the same conditions.
This behavior is due to the blocking function of the cell wall (particularly the
outer membrane and the peptidoglycan layer) that can oppose reactive species
such as holes, dOH, O2 and H2O2 produced by TiO2 photocatalyst. Following
the results shown in Figure 3.10, the corresponding data suggest that the cell
wall of the intact cell is damaged during the initial reactive step exhibiting the
lower photodegradation rate.
The process of Escherichia coli photokilling on a TiO2 film can be followed
by atomic force microscopy (Figure 3.11). Before illumination, the cells are
cylindrical (Figure 3.11a). After a short irradiation time, no major morpho-
logical change can be observed. However, the outermost layer (indicated in the
figure by ‘‘A’’), disappears after 24 h of illumination (Figure 3.11b). Indeed,
partial decomposition of the outer membrane takes place through the reactive
Figure 3.10 Survival of intact cells and spheroplasts of Escherichia coli on a TiO2 film
under UV illumination. (Reproduced with permission from ref. 17.)
species produced by TiO2. However, in the first hours of irradiation (Figure

3.11b), cell validity is not lost very effectively. Notably, the partial decom-
position of the membrane changes the permeability to reactive species, thus
enabling the reactive species to reach the cytoplasmic membrane of the cell,
with its final peroxidation (Figure 3.11c).
Stainless steel and other metals can be functionalized by a titanium dioxide
layer, with a self-sterilizing effect. This is related to important applications in
medical and cutlery and alimentary accessories in general. For instance, easily
implementable sol-gel techniques can be applied to support TiO2 on metal, as
described in Chapter 2. The survival of Staphylococcus aureus has been studied
on functionalized stainless steel and titanium.18 The results indicate that the
photocatalytic action of TiO2 is effective against bacteria (Figure 3.12). As
shown, titanium is a more effective bactericide than stainless steel. When UV
light was screened, negligible degradation occurs. UV light itself degrades
bacteria, but the effect is significantly higher in the presence of TiO2. Complete
bacterial inactivation was achieved after 60 min on stainless steel and after
90 min on titanium.
Sterilization of several objects is a primary tool in various fields of everyday
life. Thus, TiO2 can play the double role of antifogging and antibacterial
device in dental mirror surfaces routinely used by doctors. Tetraethyl ortho-
titanate can be hydrolyzed proficiently to support titanium dioxide on a
SiO2-precoated dental mirror.19 The mirror was immersed in the solution and
left to hydrolyze for different times (Figure 3.13). Water contact angles on these
glasses were measured to evaluate surface hydrophilicity. The result was a
sharp decrease, from 35.51 to less than 11, when the film was thick enough.
Reflectance was also higher than in the case of a plain mirror for any film
110
Figure 3.11 AFM (atomic force microscopy) images of Escherichia coli cells on a TiO2 film: (a) no illumination, (b) illumination for 1 day and
(c) illumination for 6 days. Radiation flux was 1.0 mW cm2. (Reproduced with permission from ref. 17.)
Chapter 3
140
(A)
120
Survival ratio [%]

100
80
60
40
20
0
0 30 45 60 90 120
UVA irradiation time [min]
250
(B)
200
Survival ratio [%]
150
100
50
0
0 30 45 60 90 120
UVA irradiation time [min]
Figure 3.12 Photocatalytic inactivation of Staphylococcus aureus on (A) titanium and

(B) stainless steel; anatase TiO2 with UV illumination (m), anatase TiO2
screened from UV light (K), irradiated naked disks (’) and naked disks
screened from UV light (&).
Figure 3.13 Appearance of a dental mirror surface with different tetraethyl orthoti-
tanate hydrolysis times: (a) 10, (b) 30 and (c) 60 min. (Reproduced with
112 Chapter 3
thickness, for both visible and UV wavelengths. Even the transparency of films
was very high (Figure 3.13).
An antibacterial effect is often needed in areas that are poorly irradiated; for
example, the areas in a room that are screened by furniture. In these cases it is
possible to load TiO2 with a small amount of doping cations that are per se able
to impart a sterilizing effect, such as Ag1 and Cu21. After an initial irradiation
with UV light these cations are reduced to the metal state in the form of
nanopowders finely adherent to TiO2 nanoparticles. This approach is extremely
efficient, especially in ensuring a permanent action, even when light does not
reach the photocatalytic material for different reasons. Some experimental
results have shown that photocatalytic tiles loaded with Ag or Cu can degrade
significant amounts of bacteria for several hours even in the dark.15
Figure 3.14, thus, shows the results obtained with the installation of pho-
tocatalytic tiles in an operating room: it is possible to see that the bacteria
present in air were reduced to negligible amounts and that the sterilizing effect
is fully retained for several months. Practically, it is possible to obtain an effect
that lasts for 24 h, which is ideal for instance in a hospital.
Following the same principles it is possible to sterilize toilets, reducing the
bad smell resulting from the ammonia and ammonia-derivatives arising mainly
from the decomposition of urine carried out by different bacteria.
Accordingly, algae and moulds growth is prevented in TiO2-covered tiles,
even under natural conditions favoring their development. It is important to
stress once again that TiO2 not only kills bacteria, but also completely
Figure 3.14 Sterilizing effect on airborne bacteria present in a hospital operating

room. (Reproduced with permission from ref. 15.)
Figure 3.15 Logarithmic reduction of microorganism population as a function of

irradiation time. (TiX indicates a polypropylene/TiO2 composite with X
wt% TiO2.) (Reproduced with permission from ref. 20.)
decomposes cells, unlike typical bactericidal agents such as silver that leave the
cell intact. This is clearly evident in Figure 3.11.
Antimicrobial polymers for food packaging applications can be prepared
by implementing a certain amount of TiO2 in an isotactic polypropylene
matrix.20 A polypropylene partially modified with maleic anhydride is
added as a compatibilizing agent to improve interfacial adhesion between the
isotactic polypropylene and TiO2. These composite materials display maxi-
mum activity for samples containing 2 wt% of anatase-TiO2 irrespective
of the microorganism. Two bacteria with different features were tested: a Gram
negative (Pseudomonas aeruginosa) and a Gram positive one (Enterococcus
114 Chapter 3
faecalis). Interestingly, both bacteria are antibiotic resistant. In both cases, the
antibacterial activity decreased with increasing TiO2 amount up to 2 wt%
(Figure 3.15). Tests performed with plain irradiation with UV-light exhibited a
negligible degradation (‘‘Control: iPP’’ in Figure 3.15).
Such functionalized polymers can open the way to a new class of materials,
i.e., photoactive food packaging, that could help in avoiding bad smells typi-
cally deriving from fish deterioration (mainly caused by trimethylamine) or
from fruits and vegetables.
References
1. (a) M. R. Hoffmann, S. T. Martin, W. Choi and D. W. Bahnemann,
Environmental applications of semiconductor photocatalysis, Chem. Rev.,
1995, 95, 69–96; (b) X. Chen and S. Mao, Titanium dioxide nanomaterials:
synthesis, properties, modifications, and applications, Chem. Rev., 2007,
107, 2891–2959; (c) I. P. Parkin and R. G. Palgrave, Self-cleaning coatings,
J. Mater. Chem., 2005, 15, 1689–1695.
2. T. Maggosa, J. G. Bartzis, M. Liakou and C. Gobin, Photocatalytic
degradation of NOx gases using TiO2-containing paint: a real scale study,
J. Hazard. Mater., 2007, 146, 668–673.
3. (a) M. Takeuchi, K. Sakamoto, G. Martra, S. Coluccia and M. Anpo,
Mechanism of photoinduced superhydrophilicity on the TiO2 photo-
catalyst surface, J. Phys. Chem. B, 2005, 109, 15422–15428; (b) M. Shi-
mohigoshi and Y. Saeki, Research and applications of photocatalyst tiles,
Photocatalysis, Environment and Construction Materials, ed. P. Baglioni
and L. Cassar, RLEM, pp. 291–297, ISBN: 978-2-35158-056-1.
4. A. Fujishima, T. N. Rao and D. A. Tryk, Titanium dioxide photocatalysis,
J. Photochem. Photobiol. C: Photochem. Rev., 2000, 1, 1–21.
5. K. Guan, Relationship between photocatalytic activity, hydrophilicity
and self-cleaning effect of TiO2/SiO2 films, Surf. Coat. Technol., 2005, 191,
155–160.
6. See, for example, Hydro-Klean Mirror by Sekisui Jushi Corporation online
at http://www.sekisuijushi.co.jp.
7. J. Kasanen, M. Suvanto and T. T. Pakkanen, Self-cleaning, titanium
dioxide based, multilayer coating fabricated on polymer and glass surfaces,
J. Appl. Polym. Sci., 2009, 111, 2597–2606.
8. C. Battaglin, F. Caccavale, A. Menelle, M. Montecchi, E. Nichelatti,
F. Nicoletti and P. Polato, Characterisation of antireflective TiO2/SiO2
coatings by complementary techniques, Thin Solid Films, 1999, 351,
176–179.
9. Details on TOP-NANO-HEGEs Coating are available online at http://
www.hege-solar.de/inovation2009.html.
10. G. San Vicente, A. Morales and M. T. Gutierrez, Preparation and char-
acterization of sol-gel TiO2 antireflective coatings for silicon, Thin Solid
Films, 2001, 391, 133–137.
11. The air mass (AM) coefficient characterizes the solar spectrum after the
solar radiation has traveled through the atmosphere. For a full explanation
see: http://rredc.nrel.gov/solar/spectra/am1.5/#about.
12. TiPEt: http://www.tipe.com.cn.
13. K. O. Awitor, A. Rivaton, J.-L. Gardette, A. J. Down and M.B. Johnson,
Photo-protection and photo-catalytic activity of crystalline anatase tita-
nium dioxide sputter-coated on polymer films, Thin Solid Films, 2008, 516,
2286–2291.
14. L. Bamoulid, M.-T. Maurette, D. De Caro, A. Guenbour, A. Ben Bachir,
L. Aries, S. El Hajjaji, F. Benoı̂t-Marquié and F. Ansart, An efficient
protection of stainless steel against corrosion: combination of a conversion
layer and titanium dioxide deposit, Surf. Coat. Technol., 2008, 202,
5020–5026.
15. A. Fujishima, K. Hashimoto and T. Watanabe, TiO2 Photocatalysis,
Fundamentals and Applications, BKC, Tokyo, 1999.
16. P.-C. Maness, S. Smolinski, D. Blake, Z. Huang, E. J. Wolfrum and
W. Jacoby, Bactericidal activity of photocatalytic TiO2 reaction: toward an
understanding of its killing mechanism, Appl. Environ. Microbiol., 1999, 65,
4094–4098.
17. K. Sunada, T. Watanabe and K. Hashimoto, Studies on photokilling of
bacteria on TiO2 thin film, J. Photochem. Photobiol. A: Chem., 2003, 156,
227–233.
18. K. Shiraishi, H. Koseki, T. Tsurumoto, K. Baba, M. Naito, K. Nakayama
and H. Shindo, Antibacterial metal implant with a TiO2-conferred pho-
tocatalytic bactericidal effect against Staphylococcus aureus, Surf. Interface
Anal., 2009, 41, 17–22.
19. K. Funakoshi and T. Nonami, Photocatalytic treatments on dental mirror
surfaces using hydrolysis of titanium alkoxide, J. Coat. Technol. Res., 2007,
4, 327–333.
20. A. Kubacka, M. Ferrer, M. L. Cerrada, C. Serrano, M. Sánchez-Chaves,
M. Fernández-Garcı́a, A. de Andrés, R. J. Jiménez Riobóo, F. Fernández-
Martı́n and M. Fernández-Garcı́a, Boosting TiO2-anatase antimicrobial
activity: polymer-oxide thin films, Appl. Catal. B: Environ., 2009, 89,
441–447.
CHAPTER 4
Photocatalytic Glass
4.1 Improving Glass Performance by
Functionalization with TiO2
The development of transparent thin coatings that impart various properties to
different kinds of glass is one of the main goals of applied research in the glass
industry at present. Typical examples are car glass and building glasses for
windows, facades, roofs, etc.
In this context, titanium dioxide is a material with outstanding properties,
such as its high optical index, refraction and transparency across the visible
wavelength range, cut-off effect towards highly damaging UV light, intrinsic
semiconducting properties, compatibility with the environment and complete
atoxicity, along with photocatalytic, anticlouding and antifogging properties.1
TiO2 thin films can also adsorb species and, hence, degrade organic and
inorganic (chemically present in a reduced form) pollutants, eventually dis-
charging their oxidation products by easy washing with plain water (even
through naturally occurring rain), thus preventing glass from fouling. In
addition, a superhydrophilic surface cannot adsorb organic oily liquids but,
instead, strongly expel them. Since TiO2 films are both photocatalytically active
and superhydrophilic, they can work in both ways (photocatalytic degradation
of pollutants on one hand and rejection of organic liquid species caused by the
superhydrophilic characteristic on one other hand). These properties arise due
to light-induced redox reactions and superhydrophilicity, the latter avoiding
the formation of rain-droplets or water vapor (Figures 4.1 and 4.2) and
favoring the free flowing of water, which washes away both dirt (such as fine
dusts) and oxidation residuals of polluting environmental agents. Environ-
mental malodorous species in air, both indoors and outdoors, are typically
present in very low concentrations, even when human sensitivity notices a very
strong smell. This is why TiO2 is an ideal species for deodorization of air;
photocatalysis works indeed unselectively by degrading almost all organics
present in the environment if adsorbed on its surface, although reaction rates
are typically very low, so that large amounts of pollutants cannot be degraded

116
Photocatalytic Glass 117
Figure 4.1 The glass shown on the left-hand side is prevented from fogging even
in a water vapor saturated environment such as the represented room.
(Photograph courtesy of Toto Ltd.)
quickly by using light and a photocatalyst. Conversely, very small amounts of

organic species can be degraded easily. If we think that common malodorous
species, such as methyl mercaptan, must be kept in concentrations lower than
0.01 ppm, it becomes clear how powerful photocatalytic devices for air
decontamination can be.2
Figure 4.1 depicts the common case of a room saturated by a high amount
of water vapor, such as in an indoor kitchen or in a particularly crowded room.
The typical fogging effect appearing on the inner side of the window glass is
absent on the left-hand glass, functionalized by a TiO2 film.
Similarly, Figure 4.2 shows (a) a car side-view mirrors (produced by Tokai
Rika) and (b) curved road mirrors under rainy conditions (manufactured by
Sekisui Jushi Corporation) when droplets of different sizes form on the surface
and remain there unless a TiO2 film activated even by a low environmental light
ensures superhydrophilicity to the surface and, thereby, prevents even fogging
effects. The result is a perfect rear-view for the driver, whose security increases
even in environmentally difficult conditions. Figure 4.2(c) shows a lamp (by
Toshiba Lighting & Technology Corporation) typically used for lighting out-
door areas at airports: its glass cover is self-cleaning and is activated by the light
emitted by the lamp.
The glass in Figures 4.1 and 4.2 has been modified through Hydrotect, a
technical brand name of Toto Ltd., by implementing a surface treatment as
part of the manufacturing process.3 The layer is perfectly adherent and trans-
parent, so that a colored surface remains esthetically unaffected by deposition.
118 Chapter 4
Figure 4.2 The right-hand part of a side-view mirror (a) and the curvet mirror on the
right in (b) are covered with Hydrotect and, hence, clouding and the
formation of water droplets are prevented. (Photograph courtesy of Toto
Ltd.) (c) The glass cover of a lamp (produced by Toshiba Lighting &
Technology Corporation) is covered with a TiO2 film. (Reproduced with
It is ideal for application in areas were hygiene matters are relevant, such as
lavatories, swimming pools and hospitals. Hydrotect has been implemented by
several companies for many ceramic and polymeric products, such as in
polycarbonate-made soundproof walls for the sides of roads.
Standard soda-lime glass, mainly made of SiO2, Na2O, CaO, Al2O3 (Table 4.1),4
amounting to more than 90% of the globally manufactured glass, can be warmed
to 500 1C, without any modification in structure. The glass transition temperature
is in fact always higher than 540 1C, depending on the treatments undertaken.
Hence supporting a TiO2 thin transparent film on glass is a rather easy matter,
because one can achieve both crystallization to the photocatalytically most active
crystalline phase (anatase) and mechanical adherence through particle sintering
and agglomeration at only 350 1C.
Films as thin as a few hundred nanometers are enough to ensure a significant
improvement in self-cleaning performance, without forgetting TiO2 intrinsic
bactericidal effect. This is particularly relevant where a sterilized environment
must be guaranteed, such as in hospital, especially in surgery rooms, laboratory
clean rooms, etc. Moreover, the antibacterial effect can be increased greatly by
doping TiO2 with noble metals.
Table 4.1 Soda-lime glass: typical composition and approximate limits
(mol.%). (Reproduced with permission from ref. 4.)
Typical container glass Typical float glass Approximate limits
SiO2 74.42 71.86 63–81
Al2O3 0.75 0.08 0–2
MgO 0.30 5.64 0–6
CaO 11.27 9.23 7–14
Li2O 0.00 0.00 0–2
Na2O 12.9 13.13 9–15
K2O 0.19 0.02 0–1.5
Fe2O3 0.01 0.04 0–0.6
Cr2O3 0.00 0.00 0–0.2
MnO2 0.00 0.00 0–0.2
Co3O4 0.00 0.00 0–0.1
TiO2 0.01 0.01 0–0.8
SO3 0.16 0.00 0–0.2
Se 0.00 0.00 0–0.1
4.2 TiO2 on Glass: More Tasks or Benefits?

Supporting a photocatalytic film on a glass substrate presents two main issues
that have to be addressed and which are not very significant for other common
ceramic materials, such as tiles: (i) the glass optical properties should not be
negatively affected by the TiO2 film; (ii) the very smooth surface of glass does
not support good adhesion, which is indeed necessary to manufacture a com-
mercial product that can be washed for years without modification of its
quality. Pretreatments to modify glass surface are possible to increase rough-
ness before depositing TiO2.
As far as deposition technologies are concerned, sol-gel precursors are
typically used in industrial production, due to the high activity of the resulting
films and good general performances in terms of mechanical resistance, light
transmittance and durability.5 The process is realized by dipping, spinning or
spraying a liquid sol on the glass, followed by a thermal treatment. The inor-
ganic or organic TiO2 precursor thus hydrolyzes and the resultant product
crystallizes in an active crystalline phase. The latter can be controlled by
changing the preparation parameters. Many other techniques are available and
present some advantages over sol-gel, but usually at much higher costs. For
instance chemical vapor deposition,6 evaporation,7 various sputtering deposi-
tions,8 and ion beam-assisted processes9 have been used successfully.
Electron beam physical vapor deposition, for example, gives very regular
films, with a tunable thickness, whereas film uniformity is less accurate when
employing sol-gel preparation. Photoactivity, conversely, is always higher in
the case of sol-gel deposition.
The use of a common glass, i.e., made not only of silica but containing sig-
nificant amounts of other oxides such as Na2O, can give limited reactivity. Thus,
supporting films on soda-lime glass can give rise to diffusion of Na1 ions during
calcination at 400–500 1C. Warming the film at high temperature is often needed to
120 Chapter 4
promote particle crystallization and aggregation, eventually resulting in fine
adhesion and photoactivity. A low Na content could act as a recombination centre
whereas higher amounts favor the formation of the brookite allotropic phase or of
sodium titanate, which is much less photoactive than TiO2 in its anatase form.10
To prevent the negative effect of Na1 ions on the photocatalytic activity,
many methods have been developed, such as precoating soda-lime glasses with
silica-based layers, thus creating a barrier layer, or implementing a glass pre- or
post-treatment with an acidic aqueous solution aimed at exchanging Na1
ions.11 Minimizing the rate of temperature increase can also reduce the diffu-
sion phenomenon, since the glass structure is less subject to thermal stress and
modification is limited. A rapid increase of temperature from 25 to 400–500 1C
can give rise to a partial softening of glass structure at the interface with TiO2,
producing sodium-titanium-oxygen compounds without any photocatalytic
activity. Figure 4.3 shows that supporting TiO2 on glass in the absence of a
Figure 4.3 Preparation processes for TiO2 films on glass substrates. (Reproduced
barrier film, and without negatively altering the photocatalytic activity, is
possible only when a highly pure glass (such as quartz) is used. Conversely,
diffusion of Na1 into TiO2 has to be prevented in the case of common glass.
Clearly, moving to high TiO2 film thickness or performing a low-temperature
preparation can assure the absence of Na1 diffusion but usually the quality (in
terms of adherence, transparence and activity) of the resulting film is not
comparable with a high-temperature preparation.
Silicon nitride has been used recently as a better barrier film than silica. For
example, a three-fold improvement in photocatalytic film activity can be
obtained by interposing a 100 nm thick SiNx film between a soda-lime glass
substrate and an anatase film. The amount of sodium present in the cross-
sectional profile of a TiO2 film is 7–8 at.% when no barrier film is present,
4 at.% when interposing a SiO2 film, and decreases to under 2 at.% when using
a SiNx film.12 Figure 4.4 shows scanning electron micrographs of the top TiO2
films before and after calcination. The TiO2 film was deposited by direct current
sputtering of a metallic titanium target in argon–oxygen reactive mixtures,
whereas the barrier films (both SiNx and SiO2) were deposited by reactive
magnetron sputtering, using a conductive boron-doped silicon target. Nitrogen
or oxygen is added to Ar for the deposition of the nitride and oxide barriers,
respectively. Calcination at 450 1C resulted in crystallization to anatase phase
and particle aggregation (Figure 4.4b and c).
Figure 4.4 SEM micrographs of cross-section (a) and top surface (b) of an amor-
phous TiO2 coating, and the cross-section (c) and top surface (d) of the
coating after annealing at 450 1C. (Reproduced with permission from
ref. 12.)
122 Chapter 4
A TiO2-modified glass has to meet different criteria to be suitable for
industrial manufacturing and commercial access to the market. Some impor-
tant attributes are needed for both application in cars and also for building
facades and windows, or for indoor applications, as previously mentioned.
The main concerns regarding a glass to be used in everyday life are listed
below:
Optical properties: the light transmittance has to be checked, because TiO2

absorbs, on the one hand, the UV fraction of solar light (a desirable
property yielding an important UV cut-off effect) but can, on the other
hand, give rise to light scattering effects with films that are either partially
inhomogeneous or too thick. An ideal film has to absorb as much as
possible UV light at lo380 nm and transmit visible light as a normal
glass. Electron microscopy and UV transmission spectra (Figure 4.5) can
give useful information about this point. Measurement of film thickness
and refractive index is also necessary and can be carried out by ellipso-
metry. Refractive index in particular is a relevant parameter: soda-lime
glass shows values of ca. 1.5, whereas that of TiO2 is about 2.5 under solar
irradiation. This is why a larger portion of the incident light can be
reflected by TiO2 with respect to glass, if the surface composition is not
well controlled. The air refractive index is indeed much lower, with a value
of ca. 1.0, and light reflection in external areas can yield undesirable
optical effects. However, nanoporous TiO2–SiO2 coatings have been pre-
pared recently with a very low refractive index, enhancing the transmission
Figure 4.5 UV–Visible transmittance spectra of TiO2 films obtained by dip-coating of

SiO2-precoated glass into sols derived from titanium tetraisopropoxide:
(a) 8, (b) 15, (c) 20 layers calcined layer-by-layer at 400 1C; (d) 15 layers
with only one final calcination at 400 1C. (Reproduced with permission
from ref. 14.)
Figure 4.6 Transmittance of bare glass and a glass coated with a double-layer TiO2–
SiO2 film. The maximum transmittance for the coated glass is over 99%.
of the glass to more than 97% for visible light (490–92% is usual for
glass) (Figure 4.6).13–15
Photocatalytic activity: photocatalytic sites have to be able to both adsorb
and oxidize inorganic and organic pollutants, washed out by natural water
or human clean up. Glass stains under outdoor conditions usually derive
from salts, silicates, carbonates, soots (inorganic species) and polycyclic
aromatic hydrocarbons, fatty acids, and long-chain alkanes. Pollutant
degradation becomes possible when TiO2 is present in an active crystalline
phase and if it is accessible to pollutants present in the gas phase. X-Ray
diffraction, along with Raman spectroscopy, can be used to identify and
quantify the crystalline phases. Biological tests can yield specific infor-
mation on the bactericidal effects of the active coating. Specific tests under
conditions simulating real ones can be carried out to study photocatalytic
activity in gas-phase reactors by degrading target compounds. Solar
(direct or diffuse) light in outdoor application is always sufficient to
activate the redox reactions, whereas a study of indoor lighting is needed
to understand if natural light is enough for activation or a specific lamp is
required. The study of photocatalytic activity is somewhat complex, since
it is influenced by many other factors, such as relative humidity, tem-
perature, kind of catalyst, irradiation type and intensity, etc.
Superhydrophilicity: this is probably the most important property for
glasses, since it allows the avoidance of fogging and droplet formation, as
previously explained, hence imparting self-cleaning features to glass.
Superhydrophilic surfaces also have another (often forgotten) property,
one that is particularly relevant for surfaces where organic liquids of
124 Chapter 4
various types can accidentally spill or be left by recondensation from air:
they are highly averse towards absorption of organic liquids, thus being
easily cleanable by plain water. This is highly desirable in kitchens or
lavatories, and also in very environmentally polluted areas, such as
industrial sites. Measurement of the water contact angle during irradiation
is important as this parameter is needed to understand the hydrophilic
properties of a film. As noted above, the study of irradiation field is
important in understanding whether superhydrophilicity is induced in a
specific environment and in glasses with a certain inclination angle (from 0
to 901).
Retention of self-cleaning properties: in a typical environment where photo-
catalytic glasses are used, their ability to keep their self-cleaning feature
should be carefully checked. Cleaning has to be performed without
aggressive detergent and avoiding strong mechanical friction that could
damage the surface. Conversely, a particularly polluted or dirty environ-
ment could result in coverage of the functionalized surface, thus hindering
physical contact between TiO2 and external agents. These phenomena are
usually easily reversible by plain cleaning, although prolonged deposition
of fine organic/inorganic particulates over the glass, left unwashed for a
very long time, could cause a temporary deactivation that is solvable only
by a significant warm-up.
As already mentioned, glass superhydrophilicity is the most important

property and, hence, several methods have been implemented to enhance per-
formances in this direction. Controlled porosity on photocatalytic films
deposited on glass can, for example, improve significantly both film hydro-
philicity and photoactivity. Adding PEG [poly(ethylene glycol)] to a sol-gel
TiO2 precursor, deposited over glass, gives rise to higher reactivity and
superhydrophilicity performance. Film calcination at 520 1C affords miner-
alization of all the carbon present, in place of which a tunable porosity is left.
The much higher number of hydroxyl surface groups present when adding PEG
can influence greatly the performance in terms of contact angle decrease.16
Figure 4.7 shows that, while there is a plateau of the hydroxyl content by
increasing the amount of added PEG (Figure 4.7a), the optimal hydrophilic
behavior is at the beginning of this plateau (Figure 4.7b). The decrease of water
contact angle from a value in the 20–401 range to 01 is indeed much faster for
sample c, i.e., the one prepared by using 0.5 g PEG. Moreover, when the light is
turned off, the contact angle value of the sample prepared in the absence of
polymer reaches its initial value fastest among all samples. This results in better
self-cleaning properties of PEG-templated samples; in fact, glass typically has
water contact angles of ca. 301, not influenced by light, whereas a much lower
angle is retained even in dark conditions for many days only by the PEG-
templated films.
Doping with transition metals is a widely investigated field, since the band
gap can be reduced and, hence, the fraction of visible light absorbed can be
Figure 4.7 Hydroxyl content (a) and contact angle variation in light and dark conditions (b) upon introducing various amounts of PEG in a
sol-gel preparation. Samples a–e were prepared by ten coating cycles from precursor solutions containing 0, 0.25, 0.5, 1.0 and 2.0 g
PEG, respectively. (Reproduced with permission from ref. 16.)
125
126 Chapter 4
enhanced. In particular, very limited Ag-doping can give bactericidal properties
to a TiO2 film even in the absence of light.
Iron-doped TiO2 films can also yield better superhydrophilic attributes.17
Both films shown in Figure 4.8, deposited through spray pyrolysis, present a
smooth surface, although the 5 at.% Fe-doped surface is less smooth than the
undoped one. Interestingly, contact angles, even under dark conditions, are
quite small (o51) both for doped and undoped samples, due to the deposition
Figure 4.8 SEM images of the surface morphology of (a) undoped and (b) 5 at.%
Fe-doped TiO2 thin films deposited by spray pyrolysis. (Reproduced with
method, while the 5 at.% Fe-doped sample reaches 01 upon irradiation much
faster than the undoped TiO2 film.
4.3 Antireflection and Composite Multilayer Films for

Advanced Applications
Composite films have been developed to improve the transmittance of visible
light of photocatalytic glasses, which is highly desirable in many applications
such as solar collectors, greenhouses and windows. Dense TiO2 films transmit,
typically, 75–85% of visible light (see for instance Figure 4.5), but work as cut-
off devices in the UV region (for l o380 nm). While the latter parameter is very
attractive since UV light is harmful for human skin, eye and immune system,
and also damages indoor objects, through photodegradation generated by
radical reactions, the low transmittance of visible light can be enhanced by
integrating antireflective properties in TiO2 films.
The high refractive index under visible radiation is responsible for this
property (Table 4.2) but attaining antireflection features is possible, for
instance, by using double layered films and tailoring their porosity, in most
cases employing TiO2 and SiO2.18
The glass reflection coefficient, or reflectance, can be calculated by the
Fresnel equation and, assuming that light is perpendicularly incident, it can be
expressed by:19
ðn0 nG Þ2
R¼ ð4:1Þ
ðn0 þ nG Þ2
where n0 is the refractive index of the medium the light is coming from (usually
air, and water in some cases) and nG is the glass refractive index. Moreover,
since light is reflected not only on the front of the glass but also on its back, and
can travel back and forth several times as well, the total reflectance through a
window is expressed as:
2R
RTOT ¼ ð4:2Þ
1þR
Table 4.2 Rough refractive index of some common substances under visible
irradiation. (Accurate values can be found in ref. 18.)
Substance Refractive index
Air 1.0
Water 1.3
Soda-lime glass 1.5
Pure silica 1.4
Titanium dioxide (anatase) 2.3
128 Chapter 4
0.9
0.8
2R/(1+R)
0.7
0.6
R
0.5
0.4
0.3
0.2
0.1
0
1 3 5 7 9 11
nG
Figure 4.9 Reflectance and total reflectance versus refractive index [see Equations
(4.1) and (4.2)].
Figure 4.9 plots R and RTOT values against nG, assuming that the medium is air
with n0 ¼ 1. It can be seen that for nG ¼ 1.5, the characteristic value of common
windows glass, the total reflectance, is ca. 8%. If we neglect absorption, non-
reflected light is transmitted, i.e., T ¼ 1 – R, and soda-lime glass reflectance is
about 92%, assuming that light rays are perpendicular to the glass.
Sol-gel methods can easily yield a low refractive index, resulting in a maximal
transmittance of 99%, which is much more than plain glass (characteristic values
are ca. 90–92%). SiO2–TiO2 films can be obtained by depositing first a silica film
from a colloidal solution and afterwards doing the same with TiO2.20 The
resulting transmission spectra are reported in Figure 4.10. Notably, silica itself
plays the role of antireflection layer with respect to nude glass (Figure 4.10b
versus a). In contrast, TiO2 alone strongly increases the glass reflection, espe-
cially in the 380–600 nm visible range, whereas for higher wavelength the dif-
ference in performance is quite low. The presence of a double-layered film,
instead, strongly enhances the transmittance of visible light, and ensures that all
the other properties typical of TiO2 films are present, resulting in self-cleaning
surfaces, which are not available with monolayered silica films.
The coupling of SiO2 with TiO2 films, however, is not the only way to attain
good antireflective properties. Extensively used as substitutes for diamonds in
their cubic phase single-crystal form, zirconium dioxide can also be coupled to
TiO2 to yield films with a low refractive index.21 Films can be prepared by a
sol-gel method, allowing the optical properties to be tailored over a wide range
by simple control of the sol composition. Figure 4.11 shows a clear decrease,
from ca. 2.3 to ca. 1.9 (at 630 nm), for films with different percentages of ZrO.
In the weak and medium absorption region, the refractive indices of the
composite ZrO2–TiO2 thin films were calculated through some relationships
employing parameters mainly derived from transmission spectra.
Figure 4.10 Transmission spectra of a bare glass substrate (a), SiO2 film (b), SiO2–
TiO2 layered films with an increasing amount of TiO2 (c)–(f ) and TiO2
films on a glass substrate (g). (Reproduced with permission from ref. 20.)
Figure 4.11 Refractive index versus wavelength for composite ZrO2–TiO2 film sam-
ples: (a) 100% ZrO2; (b) 90% ZrO, 10% TiO2; (c) 70% ZrO2, 30% TiO2;
(d) 50% ZrO2, 50% TiO2; (e) 30% ZrO2, 70% TiO2, (f ) 10% ZrO2, 90%
TiO2; and (g) 100% TiO2. (Reproduced with permission from ref. 21.)
130 Chapter 4
Figure 4.12 The Fioravanti Hidra is the first car that will not have windscreen wipers
(a), thanks to its windshield (b), which is functionalized by a four layer
film that prevents the formation of droplets and fogging, thus ensuring
perfect visibility for the driver. (Photograph courtesy of Fioravanti S.r.l.,
ref. 23.)
Multilayered films can be used for several applications by integrating the

exceptional properties of TiO2 with other technologies and materials.
Hence, the engineer Leonardo Fioravanti, previously a designer of Ferrari
cars, has designed Hidra, a hydrogen-powered car without windscreen wipers
(Figure 4.12a), that was presented at the Geneva Motor Show 2008.22,23
A four-layer film imparts self-cleaning properties to the windshield under
any environmental conditions and, notably, at any rate: it does not matter if the
car is parked or is travelling rapidly along a highway. The windshield is
moreover equipped with a hot air fan system to avoid snow deposits and hot
water is sprayed when necessary to avoid stain deposits on the glass. Moving
from outside to inside, the four thin films are constituted of:
1. a superhydrophilic layer of TiO2, to avoid the formation of droplets and

degrade volatile pollutants;
2. nanosized spherical particles to clean dirt deposits by mechanical
(nano)friction;
3. a sensor layer, detecting the presence of water over the windshield;
4. an electrical net, enabling current to reach every area of the glass
(Figure 4.12b).
The amount of current employed is very low and, indeed, is negligible

compared with the energy consumed by a car. Moreover, hot water is avail-
able to clean the most persistent dirt when the car is used after a long
parking time. Besides the already cited function, the TiO2 layer also provides
an excellent shield against the UV fraction of solar light. Fioravanti is working
on a partnership for serial manufacturing. The car could be on the market
in 2–3 years.
4.4 Industrial Overview and Commercial Products
The glass industry, along with cementitious and ceramic construction materials
industries, has probably been the most active in looking for new solutions in the
field of self-cleaning materials. Glass, in particular, is an old though still very
attractive material but all its appeal is strictly linked to its optical properties,
which decline dramatically when any kind of dust deposits on it. This explains
the strong interest of industry in developing low maintenance products in this
field.
The main sources of dust are meteorological events, essentially rain and
wind, and in urban areas also smog. Powders of different kinds can deposit on
glass, while rain absorbs all the gaseous pollutants present in air. Droplet
formation, due to the intrinsic low wettability of glass, moreover, does not
favor the leaching of soluble and particulate species. Glass forms in fact a
contact angle with water in 20–301 range, but uncleaned glass can give rise to
much higher contact angles, behaving as a truly hydrophobic material.
Taking a look at the glass industry, 62% of the international flat glass
market is, interestingly, shared among only four big companies (Table 4.3) and
Europe, in particular, shows a prominent market size of over 10 million ton (i.e.
more than 20% of the global production). The European market is largely
directed by high value-added products such as coated and laminated products,
and per capita glass consumption is around 17 kg, which is the biggest value in
the world (the United States and Japan have, for example, a per capita con-
sumption of 10 and 8 kg, respectively).24
Nowadays the market offers a wide variety of self-cleaning glasses func-
tionalized with TiO2 on sale worldwide.
Pilkington, a 200-year-old company, and member of the NSG Group
from June 2006, developed in 2001 a dedicated line of TiO2-modified glasses.
Pilkington Activt is indeed the world’ first dual-action self-cleaning glass, and
is sold in major markets worldwide. The line includes three products, covered
by a thin transparent layer of TiO2: Activt Clear, Activt Blue and Activt
Neutral, available in 4, 6 and 10 mm thickness.25
Activt Clear can be used for conservatories, roofs, skylights, covered
swimming pools and interior or exterior glass doors (Figures 4.13 and 4.14).
After the first stage of coating activation (5–7 days are typically needed), after
installation and also after each mechanical cleaning of the surface, the glass
Table 4.3 Global market share of flat glass industry in 2008. (Source:
Pilkington, ref. 24.)
Company Country Percentage of world capacity
AGC Japan 17.5
NSG Group Japan 17.0
Saint-Gobain France 15.5
Guardian United States 12.0
Others 38.0
132 Chapter 4
Figure 4.13 Application of Pilkington Activt Clear in a house (left, photograph

courtesy of Pilkington) and in a conservatory (right, photograph cour-
tesy of Oakland Group Limited).
Figure 4.14 Matsushita Denso building covered with Pilkington self-cleaning glass.
(Photograph courtesy of Nippon Sheet Glass.26)
self-cleaning properties are retained for a long time even in the presence of
cloudy weather and during the night. The second stage takes place when
rainwater hits the glass. The coatings react with ultraviolet rays present in
natural daylight to break down and disintegrate organic dirt. During the third
stage Activt Clear works as a superhydrophilic coating, thus impeding droplet
Figure 4.15 The three working stages of Pilkington Activt: (1) the coating is acti-
vated by solar light (typically, 5–7 days required); (2) light destroys
organic and many inorganic pollutants, reducing their adherence to the
glass thanks to photocatalytic effect; (3) rain washes dirt away by
forming a uniform water ‘‘sheet’’. (Reproduced with permission from
ref. 25.)
formation, so that water can spread evenly over the surface and, while running
off, take the dirt with it (Figure 4.15). Moreover, water dries off very quickly,
with respect to conventional glass, without leaving unsightly drying spots. The
reduction of glass cleaning maintenance is also a significant economic advan-
tage, especially in buildings where glass is a major component of the structure,
as in the case of skylights or conservatories. A light mechanical cleaning with a
soft cloth is sufficient and no abrasive cloth or aggressive detergents are needed.
The coating of Pilkington Activt glass, deposited during the installation
phase, is designed to last as long as the glass and re-application is not needed.
Ideal working conditions start with sloping angles of at least 101, and optimal
inclination values are around 301, but Pilkington Activt can be also used in
vertical façades and with slopes lower than 101.
Activt Blue is an attractive self-cleaning glass that evolved from Activt
Clear. It offers attractive aesthetics with its blue color and allows for solar
control and heat transmission. Compared with Activ Clear it has a significant
shading coefficient, thanks to its color, which permits indoor light regulation
also for long-wavelength light. The UV cut-off effect is comparable in both
cases. Activ Blue is, for example, ideal for conservatory roofs (Figure 4.16).
Activt Neutral is a newly developed product that is ideal even for roofs
and vertical façades. Its neutral, though slightly darker, appearance, which
134 Chapter 4
Figure 4.16 Pilkington Activt Blue allows for solar control performance and light
transmission even at long wavelengths. Its slightly blue color keeps the
inside environment cooler. (Photograph courtesy of Pilkington.25)
helps to reduce heat and light transmission, gives this product superior per-
formances to Activt Clear, especially in well irradiated areas.
Activt Blue and Neutral can be combined with a thermally insulating glass,
thus functioning as both UV and IR cut-off (Figure 4.17). This configuration
yields a comfortable temperature throughout the year in highly exposed closed
environments. In this way high energy savings for thermal conditioning can be
readily achieved. Figure 4.18 reports the performance of composite glasses
(with argon-filled cavities) of this kind compared with normal double glazing
and polycarbonate sheets. The former present much more limited light trans-
mittances, cutting the UV and IR radiation. Accordingly radiant heat trans-
mittance is low too, meaning that the warming effects caused by solar rays
are not so significant. Moreover, by considering the heat transmittance
coefficient, U, the superior performance of double glazing employing
Pilkington self-cleaning glass together with Optithermt and K Glasst, which
are two thermally insulating glasses, is obvious.
Finally, the self-cleaning features are present neither in polycarbonate nor in
normal double glazing configurations.
Figure 4.17 Pilkington Activt Blue or Neutral in double glazing configuration with a
thermally insulating glass. (Reproduced with permission from ref. 25.)
Soon after the introduction of self-cleaning glass by Pilkington (2001), the

125-year old Pittsburgh Plate Glass Company (PPG) launched a new product,
named SunCleans, implementing a durable, transparent coating of TiO2
applied during the manufacturing process.27 The transparent coating is applied
to hot glass during the forming process to produce a strong, long-lasting bond,
which makes the coating an integral part of the outer glass surface, through an
application process patented by PPG.
The product exhibits properties similar to other self-cleaning glasses: easier
maintenance is allowed by photocatalytic and superhydrophilic properties of
the coating (Figures 4.19 and 4.20). Since UV light is abundant even on cloudy
days or in shaded areas, this process works continuously throughout the day
and, after an initial activation period, even at night. The hydrophilicity makes
water droplets spread out, or sheet, across the surface of the glass. This sheeting
action also helps the window dry quickly with minimal spotting or streaking.
SunCleans is distributed to makers of wood, vinyl and aluminium windows
that can integrate this glass in their frames. Coupling self-cleaning properties
together with energy saving is also possible by employing integrated solutions
where SunCleans and thermally insulating glasses complement each other.
PPG can also provide such products, like Solarbans 70XL glass or Sungates
Low-E Glass.
The features of PPG SunCleans can be summarized as follows:
1. The glass is photocatalytic and the self-cleaning coating is activated by

UV solar rays.
136
Figure 4.18 Pilkington Activt versus normal double glazing and polycarbonate performances in terms of light and heat transmittance.
Chapter 4
Figure 4.19 PPG SunCleans compared with regular windows during raining. Water
sheeting is well apparent here. (Photograph courtesy of PPG.)
2. The glass is hydrophilic, so that the coating allows water sheeting action.
3. It offers improved thermal/optical qualities compared to regular clear
glass.
4. The self-cleaning coating is applied using PPG’ patented process.
Other benefits are:
1. UV rays work to slowly break down and loosen organic dirt on the glass
surface;
2. the glass surface dries more quickly with minimal spotting and streaking;
3. 40% reduction in UV transmittance;
4. outward appearance of the glass is slightly brighter than regular glasses;
5. solar heat gain coefficient is improved by about 0.05 points;
6. the coating is durable and long-lasting.
An overview of commercial products shows that a primary position is occupied

by Saint Gobain Glass (SGG), which is one of the three biggest glass manu-
facturers in the world. The company’ proprietary product line is SGG Bio-
clean,28 which is presented as the most neutral self-cleaning glass on the market.
The glass is not characterized by unsightly tints or reflective surfaces and
basically looks just like normal glass. Other properties are analogous to those
described for other products, thus superhydrophilic and photocatalytic prop-
erties, durability of performance and reduced cleaning maintenance are
guaranteed.
138
Figure 4.20 Scheme of PPG SunCleans working steps and comparison with regular glass. (Reproduced with permission from ref. 27.)
Chapter 4
This glass can similarly be integrated together with an appropriate inner
glass, yielding SGG Bioclean Cool-Lite ST, ideal for contemporary solar
radiation and heat transfer control. This outstanding product can hamper heat
radiation transfer from the sun to the inside of a conservatory, keeping it cooler
in warmer months (Figure 4.21). The advantages of applying such a glass can
be listed as follows:
1. neutral appearance of the roof glass matches naturally with the rest of
the conservatory glazing without compromising performance;
2. permanent dual-action SGG BIOCLEANs self-cleaning coating stays
on the glass for the lifetime of the window;
3. much easier cleaning as less dirt and grime adhere to the glass;
Figure 4.21 SGG Biocleans Cool-Lite ST is ideal for conservatory roofs. (Repro-
140 Chapter 4
4. ideal for hard to reach areas such as conservatory roofs and overhead
glazing;
5. saves on the cost of window cleaning;
6. up to 23 of heat from the sun is reflected by the advanced solar control
coating;
7. keeps conservatories cooler during sunny periods without costly air
conditioning or blinds;
8. reduces uncomfortable glare from the sun by over 50%, whilst letting in
lots of natural light;
9. 100% noise reduction compared to polycarbonate roofs;
10. provides year round comfort when combined with SGG PLANI-
THERM, a glass ensuring heat gain from the sun during cold seasons.
Competitive products are produced by Cardinal Glass Industries, a company

working on the development of residential glass for windows and doors that has
grown rapidly to more than 5500 employees located at 27 manufacturing
locations around the United States.29 Their Neatt glass is a technologically
advanced product and a commercial example of TiO2–SiO2 composite glass.
The proprietary company products compare well with some of those of the
present worldwide giants (Figure 4.22). The visible transmittance and the visible
reflectance are in fact very high and low, respectively, by comparison with the
other products. Remember that the presence of a TiO2 film can alter the optical
glass properties drastically if adequate preventative measures are not taken.
Neatt glass is exceptionally smooth thanks to a thin SiO2 layer that
improves hydrophilicity, too, by reducing significantly light reflectance. This
behavior is due to the much smoother surface of this film, compared to different
solutions (Figure 4.23). Moreover, when Neatt glass is fabricated with low-
emissivity coatings it provides ideal temperature indoors. Hence year-round
comfort can be appreciated inside the home, with an average annual energy
saving of 25%. Double-pane, tempered or laminated configurations are avail-
able in customized shapes and size.30
Figure 4.22 Wet plain glass compared with Neatt glass (left-hand panels); visible
transmittance and reflectances of Neatt glass compared to other com-
mercial glasses (right-hand panel). (Reproduced with permission from
ref. 29.)
Figure 4.23 These AFM images show that Neatt coatings (left) are much smoother than pyrolytic photoactive coatings typically used glass
surface (right). (Reproduced from ref. 30.)
141
142 Chapter 4
References
1. A. Fujishima, K. Hashimoto and T. Watanabe, TiO2 Photocatalysis.
Fundamentals and Applications, BKC, Tokyo, 1999.
2. (a) M. Schiavello, Heterogeneous Photocatalysis, John Wiley & Sons,
Chichester, 1997; (b) I. P. Parkin and R. G. Palgrave, Self-cleaning coat-
ings, J. Mater. Chem., 2005, 15, 1689–1695.
3. Toto’ Hydrotect at http://www.toto.co.jp/products/hydro/genri_en.htm
4. Statistical Calculation and Development of Glass Properties, online at
http://www.glassproperties.com
5. M. Addamo, M. Bellardita, A. Di Paola and L. Palmisano, Preparation
and photoactivity of nanostructured anatase, rutile and brookite TiO2 thin
films, Chem. Commun., 2006, 4943–4945.
6. H. M. Yates, M. G. Nolan, D. W. Sheel and M. E. Pemble, The role of
nitrogen doping on the development of visible light-induced photocatalytic
activity in thin TiO2 films grown on glass by chemical vapour deposition,
7. T. Miyata, S. Tsukada and T. Minami, Preparation of anatase TiO2 thin
films by vacuum arc plasma evaporation, Thin Solid Films, 2006, 496, 136–
140.
8. O. Treichel and V. Kirchhoff, The influence of pulsed magnetron sputtering
on topography and crystallinity of TiO2 films on glass, Surf. Coat. Tech-
nol., 2000, 123, 268–272.
9. X. Cheng, S. Hu, P. Zeng, T. Kuang, G. Xie and F. Gao, Structure and
properties of TiO2 films prepared by ion beam assisted deposition, Surf.
Coat. Technol., 2007, 201, 5552–5555.
10. (a) J. Yu and X. Zhao, Effect of substrates on the photocatalytic activity of
nanometer TiO2 thin films, Mater. Res. Bull., 2000, 35, 1293–1301; (b) Y.
Paz and H. Heller, Photooxidatively self-cleaning transparent titanium
dioxide films on soda lime glass: the deleterious effect of sodium con-
tamination and its prevention, J. Mater. Res., 1997, 12, 2759–2766.
11. (a) J. M. Herrmann, H. Tahiri, C. Guillard and P. Pichat, Photocatalytic
degradation of aqueous hydroxy-butandioic acid (malic acid) in contact
with powdered and supported titania in water, Catal. Today, 1999, 54, 131–
141; (b) H. Yu, J. Yu and B. Cheng, Facile preparation of Na-free anatase
TiO2 film with highly photocatalytic activity on soda-lime glass, Catal.
Commun., 2006, 7, 1000–1004.
12. E. Aubry, M. N. Ghazzal, V. Demange, N. Chaoui, D. Robert and A.
Billard, Poisoning prevention of TiO2 photocatalyst coatings sputtered on
soda-lime glass by intercalation of SiNx diffusion barriers, Surf. Coat.
Technol., 2007, 201, 7706–7712.
13. X. Zhang, A. Fujishima, M. Jin, A. V. Emeline and T. Murakami, Double-
layered TiO2-SiO2 nanostructured films with self-cleaning and antireflective
properties, J. Phys. Chem. B, 2006, 110, 25142–25148.
14. M. Addamo, V. Augugliaro, A. Di Paola, E. Garcı́a-López, V. Loddo, G.
Marcı̀ and L. Palmisano, Photocatalytic thin films of TiO2 formed by a sol–
gel process using titanium tetraisopropoxide as the precursor, Thin Solid
Films, 2008, 516, 3802–3807.
15. A. Fujishima, X. Zhang and D. A Tryk, TiO2 photocatalysis and related
16. X. Zhao, Q. Zhao, J. Yu and B. Liu, Development of multifunctional
photoactive self-cleaning glasses, J. Non-Cryst. Solids, 2008, 354, 1424–
1430.
17. W. Weng, M. Ma, P. Du, G. Zhao, G. Shen, J. Wang and G. Han,
Superhydrophilic Fe doped titanium dioxide thin films prepared by a spray
pyrolysis deposition, Surf. Coat. Technol., 2005, 198, 340–344.
18. E. D. Palik (ed.), Handbook of Optical Constants of Solids, Academic Press,
Orlando, 1985.
19. E. Hecht and A. Zajac, Optics, 4th edn, Addison Wesley, 2002.
20. Z. Liu, X. Zhang, T. Murakami and A. Fujishima, Sol–gel SiO2/TiO2
bilayer films with self-cleaning and antireflection properties, Sol. Energy
Mater. Sol. Cells, 2008, 92, 1434–1438.
21. L. Liang, Y. Sheng, Y. Xu, D. Wu and Y. Sun, Optical properties of sol–gel
derived ZrO2–TiO2 composite films, Thin Solid Films, 2007, 515, 7765–
7771.
22. Geneva Motor Show, online at http://www.salon-auto.ch/en
23. Fioravanti S.r.l. online at http://www.fioravanti.it
24. Pilkington and the Flat Glass Industry, 2008 report, available online at
http://www.pilkington.com/resources/pfgi2008final.pdf.
25. Pilkington ActivTM range is presented online at http://www.
pilkingtonselfcleaningglass.co.uk
26. Nippon Sheet Glass is distributor of Pilkington Active in Japan and South
East Asia (http://www.nsggroup.net).
27. PPG URL: http://corporateportal.ppg.com/ppg
28. SGG Bioclean is presented online at http://www.selfcleaningglass.com
29. Cardinal Glass Industries: http://www.cardinalcorp.com
30. Cardinal Glass Industries Neat Glass, description online at http://
www.cardinalcorp.com/data/tsb/cg/CG05.pdf
CHAPTER 5
TiO2-modified Cement
and Ceramics
5.1 Keeping Structures and Air Clean Indoors and
Outdoors
Urban buildings are often fouled by several volatile pollutants and fine dusts of
any kind present in our crowded towns. When used in a blend with a concrete
structure, TiO2 decomposes such organic fouling species, which include not
only soot, grime, oil and particulates but also biological organisms, such as
mold, algae, bacteria and allergens, and air-borne pollutants, i.e. VOCs,
including, for instance, benzene, tobacco smoke, and all the nitrous oxides
(NOx) and sulfuric oxides (SOx) that are significant factors in smog. Nitric and
sulfuric acids, formed by oxidation of NOx and SOx, respectively, are even-
tually washed away as nitrate and sulfate salts by rainwater. Chemicals causing
strong odors should not be forgotten, especially in residential areas with several
restaurants or in industrial districts.
Photocatalytic pollutant degradation can be also exploited to significantly
reduce air pollution via application of TiO2 on pavers. These modified concrete
materials are already widely used (Figure 5.1); some hundreds of square meters
have been installed in Japan, and a preliminary calculation in Harris County in
Texas estimates that a paving area costing ca. $200 is enough to destroy 1 ton of
NOx, assuming a quite limited paver duration (5 years).1
Fabrication of ceramic tiles has been another major field of application in
construction materials, both for external walls and for indoor applications
(Figure 5.2).2 In the latter case, properties such as antimicrobial and deodor-
izing ones are valuable when paving, for instance, lavatories. It has been clearly
demonstrated indeed that compounds from urine, and in particular urea, can
be degraded, and bacteria propagation inhibited. In addition, kitchens are
typical rooms where photocatalytic tiles can play an important role, by facil-
itating removal of oily compounds.

144
TiO2-modified Cement and Ceramics 145
Figure 5.1 On-site application of Noxer paving blocks. (Photograph courtesy of

Marshalls and Mitsubishi Materials Corporation.)
Figure 5.2 Photocatalytic ceramic tiles (a) in a dormitory shower room and (b)
comparison between outdoor photocatalytic/superhydrophilic (A) and
ordinary painted (B) wall tiles. (Reproduced with permission from ref. 2.)
Many other applications in construction materials are possible, such as in

tunnel walls, which quickly become dark since air flow is very difficult and smog
mounts up easily.
The use of TiO2 in construction and building materials relies on the
advantages distinctive of this semiconductor – superhydrophilicity, photo-
catalytic activity and self-cleaning properties are guaranteed. Moreover, the
concentration of characteristic pollutants in an urban environment or in tun-
nels (ranging from 0.01 to 10 ppm) is compatible with photocatalytic degra-
dation even with low ultraviolet sun radiation.
Starting in the early 1990s with the first attempts at preparing photocatalytic
concretes, the use of photocatalysts together with building materials has been
favored by the versatile features of TiO2, which, besides playing the role of
146 Chapter 5
Table 5.1 Main applications of TiO2 in construction materials.
Horizontal applications Concrete pavements
Paving blocks and plates
Roofing tiles
Roofing panels
Cement-based tiles
Vertical applications Indoor and outdoor paints
Finishing coatings
Covering precast panels
Permanent formworks
Masonry blocks
Sound-absorbing elements
Traffic dividers elements
Street furniture
Tunnels Paints and renderings
Concrete panels
Concrete pavements
Ultra-thin whitetopping
light-activated semiconductor material, is also a good structural mineral that in

addition matches well and is easily implemented in existing industrial manu-
facture of all the most common (inorganic) construction materials. These are
basically the reasons why, already in 2003, sales of photocatalytic building
materials (including glass products, tents, plastic and wallpapers, soundproof
walls – topics not discussed in this chapter) accounted for ca. 60% of the whole
photocatalytic market share in Japan.3 Table 5.1 reports the main application
of TiO2 in construction materials, divided into horizontal and vertical appli-
cations and tunnel materials.4
5.2 Merging TiO2 and Cementitious Materials

Concrete materials with TiO2 can be modified simply by dry adding a certain
amount of semiconductor. TiO2 weight percentages are in the 0.1–50% range
with respect to the binder. The resulting material is commonly used only in an
exterior layer with a thickness of ca. 1 cm and not in the entire structure, as
Figure 5.3 shows in the case of paving blocks used in a pilot (10 000 m2 large)
area in downtown Antwerp (Belgium).5 The environmental abatement of NOx
was measured in standard laboratory experiments and in situ.
Photocatalytic concrete paving blocks have been contemporaneously patent-
protected by Murata et al. (Mitsubishi Materials Corporation)6 and Cassar
et al. (Italcementi S.p.A.).7 The first includes the application of TiO2 in a
functional surface layer of a double-layer paving block with enhanced NOx-
cleaning. Parameters such as thickness, porosity or surface texture layer are all
claimed by the patent. The concentration of TiO2, use of appropriate aggre-
gates having a high NOx adsorption rate or high light transmission properties
are specified, too. Mitsubishi’s commercial product, called Noxer, recalling
Figure 5.3 Paving blocks used in Antwerp city centre (Belgium). (Reproduced with
something like ‘‘NOx killer,’’ has been specifically designed to degrade by

photooxidation exhaust automobile gases and is available in different sizes and
colors, with strength and slipping resistance equal to those of standard inter-
locking blocks. The paving works by setting up a photocatalytic reaction
between titanium dioxide contained in the top 15 mm of the block and ultra-
violet radiation from the sun. Air oxygen oxidizes NOx in the air to nitric acid.
The latter is eventually washed away and highly diluted by rain to realize active
sites for more reactions, which can take place both in dry and wet conditions.
The patent by Italcementi covers the application of appropriate photo-
catalytic particles (not necessarily TiO2) in paving tiles able to oxidize polluting
substances present in the environment. The patent describes of course the
application of the semiconductor material in terms of mass with respect to the
amount of cement or binder used. Moreover, the composition of a dry premix
containing a hydraulic binder and a TiO2-based photocatalyst is also described
in order to preserve the resulting material brilliance and color. In all cases,
anatase is indicated as the preferable crystalline phase, although Italcementi
specifies that rutile/anatase mixtures also work well, provided that a minimum
of 25% anatase is present.
Table 5.2 compares these two most relevant patents.8
Primary information when adding TiO2 powder to a concrete has to be given
about the mechanical performances of the resulting blend. Parameters such as
compressive strength, tensile strength, flexural strength and modulus of elas-
ticity of the mortars are all needed before applying a photocatalytic concrete in
buildings. Figure 5.4 shows that by increasing the semiconductor amount in
148
Table 5.2 Comparison between Mitsubishi and Italcementi patents on photocatalytic concrete materials. (Adapted from ref. 8.)
Mitsubishi Materials Corporation Italcementi S.p.A.
Patent title NOx-cleaning paving block. Paving tile consisting of a hydraulic binder and
photocatalyst particles.
Field of the NOx-cleaning paving block with enhanced efficiency of Cement composition made of a hydraulic bin-
invention fixing NOx from the air and increased pluvial NOx der dry-premixed with an additive, having
cleaning efficiency. improved property to maintain the brilliance
and color quantity, to prevent aesthetic
degradation and to degrade environmental
pollutants.
Working NOx-cleaning paving block consisting of a surface layer Use of a photocatalyst, which can oxidize in
principles that contains TiO2 and a concrete made base layer; the presence of light and air environmental
NOx-cleaning paving block with or without adsorbing polluting substances, for the preparation of a
material in the surface layer; hydraulic binder for manufacturing paving
replacement of the sand used with 10–50% of glass tiles that maintain after installation, for a
grains or silica sand having a particle size of 1–6 mm; longer time, brilliance and color quantity;
surface layer having a void fraction of 10–40% and use of a dry premix containing a hydraulic
water permeability of 0.01 cm s1; binder and a photocatalyst that can oxidize
NOx-cleaning paving block roughened with a surface in the presence of light and air environ-
roughening tool. mental polluting substances, for manu-
facturing paving tiles that maintain after
installation, for a longer time, brilliance and
color quantity.
Chapter 5
Binder Cement Hydraulic binder; white, grey or pigmented
cement; cement used for debris dams;
hydraulic lime.
Photocatalyst TiO2 without any further requirement TiO2 or a precursor thereof, mainly in the
form of anatase;
TiO2 with anatase structure for at least 25%,
50% and 70%;
blend of anatase and rutile TiO2 (70 : 30);
TiO2 doped with one or more atoms other
than Ti
TiO2 doped with one or more atoms selected
from Fe(III), Mo(V), Ru(III), Os(III), Re(V),
V(V), Rh(III);
TiO2-modified Cement and Ceramics
photocatalyst selected from the group con-

sisting of tungstic oxide (WO3), strontium
titanate (SrTiO3) and calcium titanate
(CaTiO3).
Amount of 0.6–20% by weight; 0.01–10% by weight;
photocatalyst 5–50% by weight with respect to the binder. 0.1% by weight with respect to the binder;
0.5% by weight with respect to the binder.
149
150 Chapter 5
Figure 5.4 Compressive strength, flexural strength and modulus of elasticity versus
TiO2 percentage in cement mortars. CM-a, CM-b and CM-c refer to
different TiO2 types (see text). (Reproduced with permission from ref. 9.)
a cement mortar all the mechanical properties gradually worsen, but are
still adequate for practical application.9 Conversely, the capability of NOx
adsorption shows an opposite trend. The three different curves refer to anatase
TiO2 in dry powdered form of 7 nm (CM-a) and 21 nm (CM-b) average particle
diameters, and in a colloidal suspension (CM-c) with a particle diameter of
20 nm and a density of 40%. CM-a showed the best performance in terms of
NOx adsorption, probably because of its higher specific surface area. A com-
mercial Portland was used as cement with a density of 3.13 g cm3.
Combining the traditional bituminous pavement with the proficient photo-
catalytic action of the discussed cement mortars is also possible, as recently
shown in a demonstration test.10 Common asphalt, characterized by granulo-
metry, has a degree of compactness giving rise to ca. 20% void content, with a
distribution compatible with the penetration of photocatalytic cement mortar
in the upper part of the asphalt layer; 1–1.5 cm has been found as the ideal
thickness of photocatalytic concrete over asphalt. Both manual and automatic
deposition are possible – the mortar can be induced to penetrate into the
asphalt sub-layers through scrapers working on the surface, which also ensure a
uniform distribution of the paste (Figure 5.5). The temperature has to be
lowered to 30 1C to avoid rapid evaporation that would prevent mortar pene-
tration into asphalt voids.
Compression tests made on these materials suggested that accelerants were
needed, since the mechanical performances increased slowly throughout tens of
days. Hundred cycles of water freezing/melting leave the mortar in the original
form, and no difference in performance is noticeable.
Finally, the product shown in Figure 5.5 is characterized by similar prop-
erties to that of a common asphalt (provided that an accelerant is added before
deposition), guaranteeing efficient degradation of pollutants, too.
Photocatalytic concrete has the big advantage of maintaining its clear color
for a very long time, even if the corresponding building is situated in a
very crowded and polluted town. Thus, a white cement containing TiO2
(TX Active), commercialized by Italcementi at ca. 1 h kg1, has already been
used in the construction of the ‘‘Cité de la Musique et des Beaux Arts’’ in
Chambéry, France (2001), the ‘‘Dives in Misericordia’’ church in Rome (2003)
(Figure 5.6) and for other applications in Italy and France such as the Roissy
airport in Paris and the Saint John’s Court Hotel in Monte Carlo. The
imposing structure and complex construction features of the ‘‘Dives in Miseri-
cordia’’ church built in Rome’s Tor Tre Teste district were designed by US
architect Richard Meier. The structure resembles three great sails apparently
Figure 5.5 Application of a photocatalytic mortar on a common bituminous asphalt.

152 Chapter 5
Figure 5.6 The Dives in Misericordia church (Rome) was built using photocatalytic
cement. (Photograph courtesy of Italcementi.)
swollen by an easterly wind, and consists of the actual church and the com-
munity center.
TX Active is presented by Italcementi as the perfect means to optimize the
aesthetic durability of top quality, cement-based elements.11 Once the white
cement has hardened in the form of paste, mortar or concrete, the photocatalytic
particles contained inside can oxidize organic and inorganic air pollutants in the
presence of air and light. Pollutants that can easily come into contact with the
cement, i.e., exhaust fumes, emissions from residential heating systems, indus-
trial emissions of aromatic chemical substances, and pesticides, do not adsorb
stably onto TX Active since they are oxidized to carbon dioxide. Moreover,
liquid organic pollutants do not adhere to the building materials but are washed
away by rain thanks to the light-induced superhydrophilicity of TiO2.
The use of this photocatalytic cement does not require particular caution or
specific procedures: the mortar and/or concrete preparation requires a suitable
water/cement ratio to enhance strength and prevent shrinkage; correct binder
content and adequate mixing to ensure uniform color; correct granulometric
curve; use of clean aggregates since dust particles adhering to the aggregates
can cause their removal from the binding matrix; suitable mixing time and
correct curing of casts. The concrete mix design, along with a continuous
assistance provided by Italcementi to all the customers using its photocatalytic
cement, is suitable for a wide range of applications, such as restoration projects,
building projects with complex static and aesthetic specifications, high-quality
flooring, elements produced with or without steam curing, architectural con-
crete casts, stuccos and sealings.
Recently, the two main buildings realized with TX Active have been mon-
itored to check the prolonged stability of the original color. The results for both
the Italian church and the French construction are excellent. The colorimetric
measurements were performed through a CIE L*a*b* method.12 This method
allows us to determine the colorimetric parameters for quantitative evaluation
of surface color changes. In particular, the L* parameter refers to the lightness
of luminance (included in the 0–100 range) whereas a* and b* indicate the red-
magenta and blue-yellow color-opponent dimensions, respectively. In the case
of white cement the main reference parameter is L*, which is equal to 0 for
black and 100 for diffuse white.13
Measurements were carried out during the building of Dives in Misericordia
church (in 2000) until 2006 on different points of the three sails and of the
northern wall (Figure 5.6). The differences in lightness of luminance were very
low in all cases: Table 5.3 reports in particular the values corresponding to the
external sail. The difference in b* is due to inorganic inert materials mainly
caused by sand deposition carried from the Sahara through sirocco wind. This
is confirmed by the absence of b* variation in the northern wall protected from
sirocco.
Finally, the white color of the building was preserved for 6 years with less
than 1% variation in lightness. Analogous results were recorded in Chambéry.
Table 5.4 reports the L* values along with the standard variations for the
ground floor of the main building façades. Similar results were obtained in the
other buildings and on first floor walls. Finally, a* and b* values did not change
and the sand phenomenon recorded in Rome was indeed absent.
Italcementi offers two products containing TX Active:14 the first is the binder
TX Aria, which is ideal for the preparation of paints, mortars, plasters and
concretes and can be applied in horizontal or vertical structures and in tunnels
to promote the abatement of air pollutants and improve safety. It is especially
suitable in urban and highly polluted areas. TX Arca cements are, instead, ideal
for prestigious architectural buildings, allowing preservation of both top
Table 5.3 Mean values of L*, a* and b* values corresponding to the external
sail of Dives in Misericordia church. (Taken with permission from
ref. 13.)
Year 2000 September 2003
February 2005 June 2006
(building period) (end of works)
External Internal External Internal
L* 91.75 90.81 89.37 90.44 89.68 90.31
a* –0.41 –0.11 0.30 0.06 0.44 0.05
b* 2.53 4.51 7.75 3.10 7.83 3.35
154 Chapter 5
Table 5.4 Mean values of L* and standard deviations (s.d.) corresponding to
the main building (ground floor) of Cité de la Musique et des Beaux
Arts in Chambéry. (Taken with permission from ref. 13.)
Facade orientation
West North East South
No. of measurements
Service life 26 30 26 30
(months) L* s.d. L* s.d. L* s.d. L* s.d.
t0 ¼ 0 71.5 1.8 72.0 1.6 71.6 2.0 71.3 1.6
t1 ¼ 7 71.5 1.7 71.7 1.7 71.0 1.8 71.3 1.4
t2 ¼ 15 71.7 1.7 71.6 1.1 71.8 1.4 72.0 1.4
t3 ¼ 19 71.6 1.3 71.9 1.5 71.5 1.6 71.2 2.4
t4 ¼ 26 71.3 1.6 71.4 2.0 70.8 1.5 70.4 2.0
t5 ¼ 40 71.4 2.1 71.1 1.6 70.8 1.7 70.7 1.8
t6 ¼ 56 71.3 2.1 71.5 1.9 71.3 1.5 71.1 2.0
physico-mechanical properties and their early esthetical appearance for many

years (it was used in the Dives in Misericordia).
TX Active products are commercialized also in North America by ESSROC
Cement,15 a leading North American cement producer with over 5.5 million
metric tons of annual capacity and part of the Italcementi Group.
TiO2-modified cementitious materials are not used as supporting structural
elements, since the inner non-irradiated areas would not work photo-
catalytically. Thus only an external wearing thin layer should be used.
To impart photocatalytic properties to cementitious materials it is also
possible to deposit a TiO2 sol over it by simple spray-coating. This method was
proved by the Kon Corporation (Figure 5.7), a Japanese company founded at
the beginning of the twenty-first century, producing a brand of TiO2 aqueous
sol, based on peroxide titanium photocatalysts, developed in the Saga Pre-
fecture Ceramic Research Laboratory. The Kon Corporation produces various
kinds of titanium dioxide coating products, the choice of which depends only
on the property of main interest for a specific application. Table 5.5 describes
the characteristics and weight content of different kinds of sol.16 PTA is an
amorphous sol in water medium and hence does not have any photocatalytic
function at room temperature unless it is first heated to more than 250 1C. A
very thin TiO2 film can be deposited on the surface of a substrate at room
temperature. After it is dried completely the coated film containing TiO2 can no
longer be dissolved in water. PTA-85 is suitable for spray coating whereas the
more concentrated PTA-170 is used for dip coating.
The TO series differs from PTA since it is already crystallized and shows a
strong photocatalytic activity when it is coated and dried. On a flat, smooth
surface the TiO2 coated to the substrate comes off as a powder when rubbed
with a finger because TO cannot form a hard film at room temperature.
However, the hardness of the film coated with TO can be improved when it is
heated to a certain temperature.
Figure 5.7 Aesthetics salon with exterior and indoor walls covered with a TiO2 sol.
(Photograph courtesy of Kon Corporation.)
Table 5.5 Kon Corporation TiO2 sol series. (Reproduced with permission
from ref. 16.)
Name Description Weight content (%)
PTA-85 Amorphous condition aqueous sol 0.85
PTA-170 Amorphous condition aqueous sol 1.70
TO-85 Photocatalytic active sol 0.85
TO-240 Photocatalytic active sol 2.40
TPX-85 Photocatalytic active sol 0.85
TPX-220 Photocatalytic active sol 2.20
TPX-HL Visible activated photocatalytic active sol 0.85
TPX-VB Hybrid type sol for sterilizing 0.85
TPX-AD Hybrid type sol for odor reduction 0.85
TPX-HP Hybrid type sol for superhydrophilicity 0.85
TPX is a mixed solution of PTA and TO. A film coated by TPX achieves a
photocatalytic effect and hardness of film after drying at room temperature.
TPX is a neutral solution that can be allied to various materials including metal
and resin. The photocatalytic effect and hardness of the film can be further
increased by heating the film. The resulting film is very stable over time.
The other solutions are visible-light activated (TPX-HL), hence they exploit
not only the solar UV fraction but also the visible one, which is ideal for
sterilization even in dark conditions (TPX-VB), or for destroying high amounts
of volatile organic compounds thanks to their strong adsorption on this kind of
film (TPX-AD), and, finally, the ideal film for window glass, with the highest
hydrophilicity (TPX-HP).
Many patents have been registered that describe the preparation of TiO2
colloidal solutions, even metal-doped ones to ensure a good absorption of
156 Chapter 5
17
visible light. For instance, colorless colloidal solutions can preserve the ori-
ginal appearance of a material’s surface, without altering the characteristics,
and can be applied on cementitious, marble or stone supports. The doping
agent represents an atomic percentage ranging from 0.1 to 1% with respect to
titanium atoms. Many precursors can be used, such as titanium tetrachloride,
oxysulfate or alkoxides. The hydrolysis of TiO2 precursors can take place
directly in the presence of salts containing the doping metal by co-precipitation
or mixing. The resulting liquid can be deposited by spraying or by using a
brush. Repeated depositions can be performed to reach the desired thickness.
Similarly, in 2008 A*STAR (Singapore) developed a TiO2 sol to be used as
coating for building exteriors, which has been patented and licensed to
Haruna.18
In Europe, the Italian company Global Engineering S.p.A.19 is the leader in
the development, production, certification and application of materials with
photocatalytic properties. Founded by the Milanese entrepreneur Claudio
Terruzzi, Global Engineering has launched the Ecorivestimentos trademark
into the Italian and international markets as ideal for use as a cement photo-
catalytic covering. These photocatalytic coverings have been developed with
the exclusive PPSs technology (Proactive Photocatalytic System), which was
derived from research activity carried out by the scientific partner of Global
Engineering, i.e., Millennium Inorganic Chemical (Group Cristal Global – a
worldwide leading company in the treatment of titanium). This collaboration
between the two companies has led to the development of photocatalytic water-
based paints, internationally marketed under the trademarks of Ecopitturas
and Ecopaints.
5.3 Photocatalytic Ceramic Tiles

With a difference in chemical composition, but similar in employment
with respect to self-cleaning cementitious materials, TiO2-based self-cleaning
tiles have been widely commercialized and applied. The Japanese company
Toto Ltd., in close collaboration with Professor Akira Fujishima, has regis-
tered ca. 270 patents in the photocatalytic technology domain.20 Its Hydrotect
series – aqueous suspensions containing TiO2 in powder or gel form – can be
sprayed over the surface of ceramic tiles that are in turn heated at 600–800 1C.
The resulting product shows superior superhydrophilic properties and
provides degradation of air pollutants both indoors and outdoors (see
the white tiles shown in Figure 5.2). The heat treatment is essential to
make TiO2 particles sinter and strongly adhere to the tile surface. Finally, a
thin film is formed with a thickness ranging from fractions to a few
micrometers.
The big success of photocatalytic tiles, since their appearance in 1998, has
given rise to more than 5000 projects and their introduction in the European
market. They are indeed not only produced and sold in Japan. The leading
European ceramic manufacturer Deutsche Steinzeug Cremer & Breuer AG
introduced this technology from Toto and started industrial manufacturing in
2000.21 Toto indeed transferred a technical package, including the license, some
production facilities and a supply of the coating fluid to be deposited over tiles.
The advantages of such products, guaranteed for the entire life of the tile, can
be summarized as follows:
decomposition of bacteria, fungi, algae, moss and germs,

elimination of odors,
improvement of room climate,
retention of the original characteristics of the tile such as, for example,
resistance to abrasion, resistance to chemicals, etc.,
easy cleaning,
low frequency of cleaning,
free of irritating substances, non-toxic,
environmentally-friendly,
long-term guarantee,
wide variety of products.
Areas where the tiles can be applied with great benefits (Figure 5.8) are:
catering trade and food processing,

medical areas,
swimming pools and health areas,
façades,
representative areas,
sanitary rooms.
Figure 5.9 shows how dirt is washed away by natural water (rain) or wiped
off easily by manual cleaning since it does not adhere to the ceramic. This is also
true for oil and grease, which show a natural inclination to detach from the
tiles.
Self-cleaning and stain-free performance were confirmed by many experi-
ments on site, outdoors.22 Likewise dirt and stains of oily pollutants deposited
on interior tiles used in lavatories or kitchens are always a problem. For
example, the fatty acids from soap can form chemical bonds with calcium and
magnesium in hard water and adhere to the tile surface, which are difficult to
clean after the accumulation of dirt.23 Hence the role of the TiO2 film inter-
posed between the ceramics and the organic dirt surface can break their
binding, rendering the washing process much easier (Figure 5.10).
Photocatalytic activity has to be checked with care since (i) the catalyst
properties have to be preserved during the manufacture and (ii) its accessibility
to both the organic compounds and to sufficient UV-light have to be verified.24
Superhydrophilicity, on one other hand, is promptly promoted when
exposing the surfaces to light, but can be highly prolonged even in dark con-
ditions by combining TiO2 with SiO2 or other silicon compounds with siloxane
158
Chapter 5
Figure 5.8 Application areas of ceramic tiles. (Photograph courtesy of Deutsche Steinzeug/brand Agrob Buchtal.)
Figure 5.9 Functionalization of simple ceramic tiles (a) with TiO2 (b) ensures superior
performances by avoiding drop formation and promoting the abatement
of air pollutants. (Photograph courtesy of Toto Ltd.)
Figure 5.10 Dirt does not adhere to the photocatalytic tiles and is easily wiped off
(a); oily liquids that do not have any affinity with the TiO2 film readily
detach (b). (Photograph courtesy of Deutsche Steinzeug/brand Agrob
Buchtal.)
bonding.25 Consequently, a right balance between photocatalytic oxidative

activity (decreased by silica) and superhydrophilic effect should be found.
Application of photocatalytic ceramic tiles can ensure a relevant steriliza-
tion, thanks to their antimicrobial features. Figure 5.11 shows how a photo-
catalytic tile can decompose bacteria such as Escherichia coli, once they adsorb
160 Chapter 5
Figure 5.11 Bactericidal activity of photocatalytic tiles is clear for all three bacteria
shown. (Reproduced with permission from ref. 2a.)
on its surface. This effect becomes much stronger when TiO2 is doped with
silver or copper nanoparticles. Doping with silver and copper ensures, more-
over, a modest antimicrobial activity even in the absence of light, so it is
strongly advised when the bactericidal effect is important even in shadowed
surfaces such as in hospitals.
Other useful properties, verified indoors, are the decomposition of
cigarette smoke and of organic compounds present in urine. On this basis, the
Italian company Gambarelli has developed a complete series of ceramic tiles
made of porcelain stoneware for all rooms of a flat and for outdoor use. Their
brand name Oxygena26 refers to the role played by the active oxygen that
promotes the bactericidal and antismog effects. Oxygena ceramics are protected
by an international patent deposited in 2003, where the major innovation lies in
the firing system. Indeed, while TiO2 loses its photocatalytic properties at
900 1C Gambarelli has succeeded in creating a firing system that prevents the
loss of anti-pollution properties, enabling the tiles to be fired at 1130 1C, thus
ensuring the best qualities of mechanical strength along with those of anti-
pollution.
A test protocol has been drawn up that demonstrates that 1 m2 of Oxygena
tiles exposed to daylight eliminates in eight hours pollutants such as NOx,
purifying a volume of air as high as 72 m3.
The only by-products are very small quantities of salts that are easily
removed by wind and rain outside or a simple washing indoors. Several hotels,
touristic villages, fitness centers, airports and also privates have already chosen
Oxygena.
Before entering the market, these ceramics were tested by simulating the air
quality of towns such as Rome or Milan in the laboratory. Gas containing
nitrogen monoxide and dioxide was fed into glass domes placed over a titanium
dioxide tile. The concentrations were in the 1–10 ppm range, corresponding to
medium-high and very high pollution levels. Lamps reproducing the solar spec-
trum were used to simulate radiation by sunlight. The clear result has been that
the quantity of pollution left was by far lower than the gas pumped in at the
beginning of the experiment. This gives a direct and clear relation between the
effect of the tiles and the reduction of pollution. Regarding indoor application, the
activating effect lies in daylight and works when windows are present in a room. It
is, however, possible to install a lamp emitting near-UV light in the case of rooms
without windows. When turned on for a few hours during the night it manages to
clean the tiles and air through activation of photocatalytic reactions. Even
ordinary lamps used for lighting activate the reaction, even if in a limited way.
Figure 5.12 shows some of the porcelain stoneware tiles proposed by
Gambarelli. Both the glazed version and the more traditional full body type are
produced and sold under the Oxygena brand.
Figure 5.12 Porcelain tiles of the Oxygena series range from traditional style to
modern and parquet-like. (Photograph courtesy of Gambarelli.)
162 Chapter 5
Figure 5.13 Dahlia Designs ceramic tiles are ideal in kitchens and bathrooms.
(Photograph courtesy of Dahlia.)
Dahlia produces and sells in Singapore ceramic and glass tiles functionalized
with nanosized anatase TiO2 with particular emphasis towards application in
baths and kitchens.27 After spending many years on research, Hongsheng
Ceramics (Suzhou Industrial Park) Co. Ltd. has successfully developed tita-
nium dioxide coated ceramic tiles (Dahlia Designs), without compromising the
exquisite finish of the ceramic tiles. They claim that the photocatalytic coating
gave rise to a new generation of self-cleaning, antibacterial, antifungal crystal
glass tiles and ceramic tiles, meeting expectations of a high standard of living,
environmental quality of the surrounding space and everyone’s wish to live in a
comfortable, clean and healthy environment. These tiles, which show major
anti-abrasion properties, also proved to be bactericidal and to degrade volatile
benzene under solar irradiation. Figure 5.13 shows an application of Dahlia
tiles in a cooking area. Dahlia has also recently launched a new series of pro-
ducts with highly vibrant colors in the shape of crystal glass mosaics, and
sparkling glass.
Tiles indoor and on façades are not the only applications of photocatalytic
ceramic materials. Roof-tiles have indeed been commercially developed by the
German company Erlus, in a vast variety, different in shape, size and color (red,
brown and black) (Figure 5.14).28 The product name is Erlus Lotus, and it is
the first self-cleaning clay roof, destroying organic dirt particles such as fat
deposits, grime, moss and algae using sunlight. Rain washes away the residuals
produced from reaction. In 2004 this product line won the Materialica Design
Award in the category of ‘‘materials.’’
Figure 5.14 Erlus available roof-tiles (a) and an example of a roof with Erlus Lotus
self-cleaning tiles (b). (Photograph courtesy of Erlus.)
5.4 New Concepts

Two relevant inconveniences when depositing a layer (commonly 0.3–1.5 cm
thick) of photocatalytic concrete over a substrate are that (i) reactions and
diffusion of products can take place from this layer to the substrate material,
164 Chapter 5
Figure 5.15 Pathways of light and activation of TiO2 in a concrete surface layer using
glass as aggregate. (Reproduced with permission from ref. 30.)
which can undergo damage, and (ii) only a small fraction of the employed TiO2
truly works photocatalytically, since most of it is not reached by irradiation.
The former problem can be solved by using a thin layer of inert silica that can
work as a proper barrier against ionic and molecular compound diffusion.29 To
enlarge the active semiconductor surface and hence the amount of pollutants
destroyed in a given area, we should work to make solar rays reach as much
catalyst as possible.
The replacement of the high amount of sand used in the preparation of
concrete with recycled glass cullets is surely an interesting way to achieve this
aim.30 Thanks to the transparency of glass, light rays can indeed penetrate
through a higher thickness with respect to normal concrete, where SiO2 particles
give rise to significant light scattering. Light is thus reflected by glass and the
pathway of rays is longer than in the presence of sand (Figure 5.15). Moreover,
the use of recycled material is of sound added value to this composite material.
The positive influence of transparence has been confirmed by comparing
performances of colored and transparent glass of similar sizes. Hence, lightly/
mildly colored glass or clear glass performs better than strongly colored ones
and brown glass performs even worse than sand (Figure 5.16).
Finally, glass particle size is not an important factor, probably because
compaction is necessary in concrete preparation.
TiO2 can be efficiently supported by impregnation on porous supports such as
pumice stone.31 Such techniques allow one to adsorb as much as 50 g m2 of
catalyst on pumice stone pellets. The latter, being soft materials, have to be fixed
on a hard matrix such as cement before its hardening. The resulting materials
can easily constitute construction materials and degrade air pollutants. The
porosity of the described pellets is a smart means of enhancing photoreactivity.
On one other hand, deposition of TiO2 over glazed ceramic tiles can be
achieved through screen-printing, a very cheap technique that is well estab-
lished in different manufacturing fields, from textile to glass and ceramics
industry. TiO2 nanoparticles can be firstly suspended in an organic solvent and
Figure 5.16 Comparison of NO removal by samples containing different colored

glass and sand under the same experimental conditions. (Reproduced
Figure 5.17 Eco-life-type houses using self-cleaning photocatalytic materials.

(Photograph courtesy of PanaHome.)
then deposited. A final calcination at high temperatures (4300 1C) imparts

strong adhesion and all the properties characteristic of TiO2 films. The results
in terms of structure, agglomeration size, and crystalline phase strongly depend
on calcination temperature.32
The integrated application of photocatalytic tiles together with cement
and glass yields exceptional buildings, such as the Eco-life homes shown in
Figure 5.17, realized by PanaHome, a housing company within the Panasonic
Group.33 These houses are designed with the following features:
safety and security: highly durable structures ensuring safety with their
high earthquake resistance, obtained by using special kinds of strong steel-
frame structures;
health and comfort: by using wind power and natural materials, the quality
of air is improved, combining mechanical and natural ventilation, whereas
humidity is controlled by means of natural materials absorbing and
emitting moisture;
166 Chapter 5
energy generation and conservation: solar power generation systems are
integrated in roofs or façades, and a self-cleaning effect brought about by
the photocatalytic technology keeps the outer wall of the house clean, at
the same time degrading air pollutants.
References
1. D. H. Chen, K. Li and R. Yuan, Photocatalytic Coating on Road Pave-
ments/Structures for NOx Abatement, presented to Houston Advanced
Research Center, available online at http://files.harc.edu/Projects/
JointCenter/Meetings/RR200512/ProjectPhotocatalyticCoating.pdf.
2. (a) A. Fujishima, K. Hashimoto and T. Watanabe, TiO2 Photocatalysis.
Fundamentals and Applications, BKC, Tokyo, 1999; (b) A. Fujishima,
X. Zhang and D. A. Tryk, TiO2 photocatalysis and related surface phe-
nomena, Surf. Sci. Rep., 2008, 63, 515–582.
3. A. Fujishima and X. T. Zhang, Titanium dioxide photocatalysis: present
situation and future approaches, C. R. Chim., 2006, 9, 750–760.
4. L. Cassar, A. Beeldens, N. Pimpinelli and G. L. Guerrini, Photocatalysis,
Environment and Construction Materials, ed. P. Baglioni and L. Cassar,
RILEM, 2007, p. 131, ISBN: 978-2-35158-056-1.
5. A. Beeldens, ed., Photocatalysis, Environment and Construction Materials,
P. Baglioni and L. Cassar, RILEM, 2007, p. 187.
6. Y. Murata, H. Tawara, H. Obata and K. Murata, NOx-cleaning paving block,
EP-patent 0 786 283 A1, Mitsubishi Materials Corporation, Japan, 1997.
7. L. Cassar and C. Pepe, Paving tile comprising an hydraulic binder and photo-
catalyst particles, EP-patent 1 600 430 A1, Italcementi S.p.A., Italy, 1997.
8. G. Hüsken, M. Hunger and H. J. H. Brouwers, Experimental study of
photocatalytic concrete products for air purification, Build. Environ., 2009,
44, 2463–2474.
9. M. Kawakami, T. Furumura and H. Tokushige, Photocatalysis, Environ-
ment and Construction Materials, ed. P. Baglioni and L. Cassar, RILEM,
2007, p. 163.
10. M. Crispino and S. Lambrugo, Photocatalysis, Environment and Con-
struction Materials, ed. P. Baglioni and L. Cassar, RILEM, 2007, p. 211.
11. Details of TX Active cement are presented (in Italian) online at http://
www.italcementigroup.com/NR/rdonlyres/5A1BE31D-49DE-4C7C-9B95-
B49C8DE9F1A7/0/Comunicato_TXActive_EN.pdf
12. Report of Committee on Colorimetry, J. Opt. Soc. Am., 1944, 34, 633.
13. G. L. Guerrini, A. Plassais, C. Pepe and L. Cassar, Photocatalysis, Environ-
ment and Construction Materials, ed. P. Baglioni and L. Cassar, RILEM,
2007, p. 219.
14. TX Arias and TX Arcas are presented at http://txactive.us/product.html
15. ESSROC Cement: http://www.essroc.com/
16. Kon Corporation products are described online at http://www.saga-kon.
co.jp/english/product.html
17. R. Amadelli, L. Cassar and C. Pepe, Use of photocatalytic preparations of
colloidal titanium dioxide for preserving the original appearance of
cementitious, stone, or marble products, US Patent 6824826, Italcementi
S.p.A., Italy, 2004.
18. A*STAR press release at http://www.nanotech-now.com/news.cgi?story_id ¼
31500
19. Information about Global Engineering products is available online at
http://www.globalengineering.info/index.php?idx ¼ prodotti
20. Toto Ltd. patents: http://www.toto.co.jp/docs/hyd_patent_en/case_001.htm
21. A products brochure is available online at http://www.deutsche-steinzeug.
de/en/hydrotect_new/grafik/Hydrotect_GB.pdf
22. See, for example, R. Wang, K. Hashimoto, A. Fujishima, M. Chikuni,
E. Kojima, A. Kitamura, M. Shimohigoshi and T. Watanabe, Photo-
generation of highly amphiphilic TiO2 surfaces, Adv. Mater., 1998, 10, 135.
23. J. Chen and C. Poon, Photocatalytic construction and building materials:
from fundamentals to applications, Build. Environ., 2009, 44, 1899–1906.
24. D. M. Tobaldi, A. Tucci, G. Camera-Roda, G. Baldi and L. Esposito,
Photocatalytic activity for exposed building materials, J. Eur. Ceram. Soc.,
2008, 28, 2645–2652.
25. M. Shimohigoshi and Y. Saeki, Photocatalysis, Environment and Con-
struction Materials, ed. P. Baglioni and L. Cassar, RILEM, 2007, p. 291.
26. Information about the Oxygena brand can be found online at http://
www.gambarelli.it/catalogue/pdf/Catalogo_Tecnico_Oxygena.pdf
27. Information about the Dahlia Designs brand can be found online at http://
www.asiadynasty-dahlianano.com/en/index.php?option ¼ com_content&
view ¼ article&id ¼ 128:photocatalyticproperty&catid ¼ 58:setsco-test-
report&Itemid ¼ 182
28. Information about the Erlus Lotus brand can be found online at http://
www.erlus.de/rooftilemodels/lotus/
29. T. Yuranova, V. Sarria, W. Jardim, J. Rengifo, C. Pulgarin, G. Trabesinger
and J. Kiwi, Photocatalytic discoloration of organic compounds on out-
door building cement panels modified by photoactive coatings, J. Photo-
chem. Photobiol. A: Chem., 2007, 188, 334–341.
30. J. Chen and C.-S. Poon, Photocatalytic activity of titanium dioxide mod-
ified concrete materials – influence of utilizing recycled glass cullets as
aggregates, J. Environ. Manage., 2009, 90, 3436–3442.
31. K. V. Subba Rao, A. Rachel, M. Subrahmanyam and P. Boule, Immobi-
lization of TiO2 on pumice stone for the photocatalytic degradation of dyes
and dye industry pollutants, Appl. Catal. B: Environ., 2003, 46, 77–85.
32. P. S. Marcos, J. Marto, T. Trindade and J. A. Labrincha, Screen-printing
of TiO2 photocatalytic layers on glazed ceramic tiles, J. Photochem. Photo-
biol. A: Chem., 2008, 197, 125–131.
33. Information about Eco-life homes can be found online at http://www.
panahome.jp/english/ecolife/index.html
CHAPTER 6
TiO2 on Plastic, Textile, Metal

and Paper
6.1 TiO2 Supported on Plastic Materials
The preparation of photocatalytic polymers is an attractive field, in which some
results have already been obtained, with a few commercial materials available
on the market. The application of such light, sometimes flexible and cheap
products is very wide and ranges from household appliances, to the automobile
industry, soundproof road barriers, tents for outdoor applications (e.g., gaze-
bos) to various indoor functions. Figure 6.1 shows a sample present in the
‘‘Photocatalyst Museum’’ at the Kanagawa Academy of Science and Tech-
nology. The tent material, produced by Taiyo Kogyo, is made of a PVC film
coated with TiO2 photocatalyst on the left-hand half. The pictures were taken
in 2004 and 2007 and it is clear how outdoor exposure to smog has dirtied the
right-hand uncovered area.1
The methods used to obtain such materials are several and varied.2 The first
point that should be stressed is the huge chemical difference between titanium
dioxide and polymeric materials. The former is an inorganic mineral, organized
in a crystalline structure, whereas polymers are mainly made of organic
monomer units with a complex organization and vary one from another.
Needless to say, the physicochemical affinity between TiO2 and (generally
speaking) plastics is usually very low. This is why supporting TiO2 on polymeric
materials is challenging; another primary reason resides in the impracticality of
warming at high temperature to afford titanium dioxide crystallization (if the
deposited film is an amorphous film) or particle sintering (if powdered TiO2 is
supported) and thus a good adhesion to the substrate. Polymers are thermo-
labile and cannot be treated at temperatures above 200 1C, otherwise their
structure undergoes irreversible modifications giving rise to poor mechanical
and physicochemical properties.
Introducing TiO2 crystalline particles during a polymer synthesis is not a
good way of obtaining a photocatalytic material, for different reasons: on one
hand we should use significant percentages of inorganic material, thus

168
TiO2 on Plastic, Textile, Metal and Paper 169
Figure 6.1 PVC material manufactured by Taiyo Kogyo and kept outdoors. The left-
hand half part of the tent material was coated with TiO2. Picture taken: (a)
22 July 2004; (b) 23 April 2007. (Reproduced with permission from ref. 1.)
drastically affecting the final polymer characteristics; on one other hand, TiO2
particles, even if surrounded by a thin polymeric films, do not come into
contact with target pollutants present in air or water and no redox reaction
occurs. Another effect that should not be neglected is the thermal catalytic
activity of TiO2, which can radically affect the reaction of monomers if the
polymerization is carried out at certain temperatures.
It is, however, possible to spray-coat room temperature curable resins with
TiO2 particles to obtain a photocatalytic external layer. For instance, Smooth-
On Crystal Clears 202, a low viscosity urethane resin that cures at room
temperature with negligible shrinkage, can be functionalized by spraying with
Degussa P25 particles during resin curing.3 Samples had to be washed because a
significant amount of excess powdered TiO2 remained on the resin surface.
SEM images revealed that the TiO2 layer was quite thick, up to 70 mm, and it
depended on the application moment with respect to curing development. The
described coating method works mechanically rather than through chemical
bonding, and thus requires a certain degree of TiO2 particle encapsulation. By
tailoring experimental conditions it should be possible to avoid encapsulating
all of the TiO2, which would prevent it participating in reactions with pollutants
in the reaction medium (either air or liquid phases). These materials have been
tested for propene gas phase oxidation under UV irradiation, performed with a
medium-pressure mercury lamp. Acetone, CO, H2O and CO2 were detected as
oxidation products. Even though this process has been applied to room curable
polymer resins, it could be similarly extended to other polymeric materials. A
key factor influencing the properties of the final material is the time at which the
coating is applied during the resin curing process, which eventually determines
the thickness (Figure 6.2) and quality of the TiO2 layer.
If we choose to support a film by, for example, means of a sol-gel method,
this implies that the deposited titanium dioxide film has to be either crystalline
or warmed at 400 1C to obtain a crystalline photoactive structure, and the same
temperature should be reached if we use titanium dioxide crystalline particles
170 Chapter 6
80
Layer thickness [µm]

60
40
20
0
30 40 50 60 70 80
Coating time [min]
Figure 6.2 Thickness of TiO2 film spray-coated on Smooth-On Crystal Clears 202
resin with respect to coating time. Time zero is represented by the
beginning of resin curing. (Reproduced with permission from ref. 3.)
along with an organic gluing template, in order to get rid of the organic species
and to obtain, mainly, particle sintering. Nevertheless, the hydrolysis of tita-
nium alkoxides, carried out at moderate temperatures (40–100 1C), can yield a
crystalline anatase structure without the need for calcination. For instance,
acrylonitrile–butadiene–styrene polymer (ABS) and polystyrene (PS) substrates
have been covered by means of a TiO2 transparent nano-sol.4 The latter was
obtained by hydrolysis of titanium tetraisopropoxide in isopropanol, acet-
ylacetone and water. The eventual addition of nitric acid and warming at 80 1C
made the hydrolysis complete, modifying the complexing power of the inhi-
biting ligand (acetylacetone) and providing some thermal energy favoring the
structural reorganizations needed for crystallization of TiO2 nanoparticles. The
final transparent sol (applied by dip-coating) showed different transmittance
spectra depending on TiO2 amount (ranging between 0.3 and 3 wt%) and
acetylacetone/Ti ratio (Figure 6.3).
Film quality is strongly influenced by some parameters, such as the
number of coating cycles. By increasing this number from 5 to 10, the
surface starts to crack and deep pores appear with increasing film thickness.
This behavior can be ascribed to the large mass change during volatilization of
solvent and acetylacetone. Similarly, the increase of TiO2 content pro-
duces severe cracks and pores on the surface of the films. The adhesion of films
was tested in various ways and found to be satisfactory. Indeed,
even treatments with organic solvents did not give rise to film peeling. The
photocatalytic activity of these films was evaluated by decomposing Methylene
Blue.
Notably, methods involving the hydrolysis of a titanium alkoxide to yield a
transparent sol with a certain degree of crystallization hardly ever permit TiO2
amounts higher than 10%.
Polycarbonate and poly(methyl methacrylate) substrates have also been
functionalized by spin-coating of a sol derived from titanium tetraisopropoxide
Figure 6.3 Variation of UV–Vis spectra of TiO2 hybrid sols with complexing ratio
(acetylacetone/Ti ¼ x); x ¼ (a) 0, (b) 1, (c) 2 and (d) 3. Inset: corresponding
optical absorption spectra. (Reproduced with permission from ref. 4.)
hydrolysis in ethanol, water and hydrochloric acid.5 Once deposited, the films
were heat-treated in an autoclave placed inside a tubular furnace at 90–140 1C.
This treatment was carried out in the presence of ethanol–water vapors. Water/
ethanol ratios (rwe) between 0 and 100 were tested. Anatase crystals (ca. 10 nm)
were obtained along with traces of brookite, detected by means of selected area
electron diffraction patterns, and, notably, autoclaving time strongly influences
both refractive index and thickness (Figure 6.4). As crystallization proceeds,
the refractive index was observed to decrease. This behavior is related to a
continuous increase in porosity. Moreover, it should be underlined that the
refractive index value of autoclaved films was very low compared to the value
measured on films heat-treated in air.
The photocatalytic activity of these films was studied through malic acid
photodecomposition tests. All the autoclaved films showed a constant rate of
malic acid disappearance over a period of 3 h, thus indicating apparent zero-
order kinetics. To obtain a proper indication of photoactivity, films autoclaved
for 5 h in the range 90–140 1C were compared with others of similar thickness
that had been heat-treated in air for 1 h at 300 and 500 1C by using a silicon
substrate (instead of a polymeric one). The anatase crystallized film heat-
treated at 500 1C transformed about 30% of the malic acid after 3 h UV
exposure. With respect to this film, the photocatalytic yield of autoclaved films
was about 50%.
172 Chapter 6
Figure 6.4 Thickness and refractive index versus autoclaving time for TiO2 films spin-
coated as described in the text. Untreated film accounts for a film dried
only at room temperature for 24 h. The drawn lines simply show the trends
and do not represent any studied model. (Reproduced with permission
from ref. 5.)
The low affinity between the polymeric substrate and TiO2 can be moderated
by implementing chemical treatments to perform a surface functionalization of
the polymeric interface or by choosing a polymer with appropriate functional
moieties. For instance, sulfonic groups of a Nafion film were reported to
enhance TiO2 anchoring thanks to the mutual electrostatic interaction.6 Thus,
the resulting thin film photocatalyst showed stable performance during long-
term operation, without TiO2 leaching from the polymer surface, providing
acceptable kinetics during the photocatalytic degradation of an azo dye.
TiO2 can also be bound on inert thin polymer films without charged groups
(such as sulfonic, carboxylic or phosphonic) able to interact electrostatically
with the TiO2.7 Thus, heating Tedlars, Parylene or low density polyethylene
films, inside an alcoholic suspension of TiO2 particles, introduces oxidative
binding sites on the polymer surface that properly anchor TiO2. The resulting
materials are shown in Figure 6.5 in which Degussa P25 TiO2 nanoparticles are
clearly visible. Notably, the layer of TiO2 particles on the polymeric film after
ca. 6 h reaction was found to be quite stable, thus explaining the long-term
activity of the materials under irradiation. Photocatalytic degradation of two
dyes (Methyl Orange and Orange II) was tested in aqueous solution irradiated
by simulated solar light. Significant differences were found, depending on the
polymeric substrate used; the kinetics of the Tedlar/TiO2 and Parylene/TiO2
photocatalyst for azo-dyes degradation were about twice that of polyethylene/
TiO2. These materials were able to resist highly oxidizing hydroxyl radicals and
to give rise to photocatalytic reactions. However, many aspects of either phy-
sical or chemical binding have still to be investigated.
Polycarbonate substrates can be functionalized with TiO2 by direct current
reactive magnetron sputtering. This method has several benefits, such as
Figure 6.5 Transmission electron microscopy (TEM) of (a) a TiO2/low density

polyethylene film and (b) a TiO2/Tedlar film before use in the photo-
catalytic reaction. ‘‘Epoxy’’ indicates a resin polymerized at 60 1C over the
film before TEM analysis. (Reproduced with permission from ref. 7.)
applicability to large-areas, even in industrial productions, and can be applied

at room temperature. The resulting films are poorly crystalline, but they are
photocatalytically active. Polycarbonate is one of the most used thermoplastics,
with applications mainly in the construction and automotive industry due to its
excellent impact resistance, low weight and transparency. Examples of objects
where polycarbonate can be found are building roofs and windows, car roof
elements, automotive headlamps and ophthalmic lenses. As far as the appli-
cation method is concerned, total sputtering pressure has a prominent effect on
the film microstructure, light absorption and photocatalytic activity of the
resulting TiO2.8 The doping effect of iron has been studied, along with the
influence of substrate (polycarbonate versus glass). UV–Vis transmittance
(Figure 6.6) gives useful information when comparing different doping
amounts and substrates. In Figure 6.6 samples B are made of pure TiO2,
samples C are moderately iron-doped films (ca. 0.6% Fe) and samples D are
highly doped films (ca. 2.5% Fe). Absorption edges of Fe-doped TiO2 films are
clearly shifted to the visible region with increasing iron concentration, indi-
cating the greater light absorbance of Fe-doped films. Highly doped films
(sample D) show the lowest transmittances (at 550 nm) for both glass and
polycarbonate substrates. Scattering loss instead is higher for iron-doped
samples, probably because of their high roughness. This characteristic could
also be responsible for the low transmittances when compared with pure TiO2
films.
Rhodamine B was degraded by using all samples as the catalysts under UV
irradiation. By using both substrate materials, the photocatalytic activity of
174 Chapter 6
Figure 6.6 UV–Vis transmittance of DC magnetron sputtering deposited TiO2

films on polycarbonate and glass. Sample B indicates pure TiO2; samples
C and D have increasing iron content. (Reproduced with permission from
ref. 8.)
pure TiO2 films deposited at low sputtering pressure was prominent. Such films
exhibit small grain size, indicating that the lifetime of free electron–hole pairs
are particle-size dependent. Hence the number of free charges on the TiO2
surface should be reduced, resulting in improved photocatalytic activity.
Moderate concentrations of iron dopant yield a slight increase in photo-
catalytic activity with respect to pure TiO2 films deposited under the same
experimental conditions. Conversely, a high iron concentration is detrimental
for photocatalytic efficiency. Finally, comparison between the photocatalytic
activity of TiO2 films deposited on polycarbonate and glass substrates shows
that the polymeric material is more active. Hence, polycarbonate appears a
promising material in terms of its photocatalytic properties, with a view to
industrial application as a low-weight ‘‘self-cleaning’’ material.
As mentioned briefly already, a key aim when preparing a photocatalytic
polymer is to retain its mechanical properties. Films deposited through room
temperature magnetron sputtering on polycarbonate have been tested by
applying a test velocity of dl/dt ¼ 0.2 mm min1 on the sample strips. Similarly,
some samples were prepared for the photocatalytic experiments after strain
deformations of 0.5%, 1% and 5%.9 Figure 6.7 shows typical stress–strain
curves for polycarbonate substrates. Young’s modulus for polycarbonate
substrate was measured as B8.4 MPa and for the composites materials 8.9–
9.5 MPa. Hence, the mechanical performance of the composite materials
improve, because the Young’s modulus of TiO2 is rather high if compared to
Figure 6.7 Stress–strain curves for polycarbonate samples nude and functionalized by
TiO2. The different curves correspond to the maximum strain deformation
applied to each of the samples for the photocatalytic experiments.
polycarbonate one. Its value ranges in fact between 0.7 and 1.8 GPa for
deposited films that are ca. 600 nm thick and poorly crystalline.
Variations in microstructure with the applied axial strain were observed by
an optical microscope connected to a CCD camera (Figure 6.8). In all cases
visible cracks only appeared for samples deformed at strains larger that 0.75%.
Samples prepared with oxygen flow rates before the threshold conditions (A-
type) had a better mechanical performance than those prepared with a com-
position slightly above it (B-type). In the A-type samples the cracks appeared,
indeed, at quite larger deformation (B1.5%) than for B-type samples
(B0.76%).
Interestingly, in the degradation of Rhodamine B the most deformed sam-
ples showed the highest degradation rates. In fact, as the material is deformed
and cracks propagate it exposes more surface area than previously and, thus,
the UV-generated electron–hole pairs have more sites at which to reduce/oxi-
dize the pollutant.
A multilayer spin-coating procedure has been applied to deposit TiO2 on
thermoplastics such as high-density polyethylene (HDPE) and poly(vinyl
chloride) (PVC).10 These polymers are among the most widespread worldwide:
HDPE is processed, by blow molding or injection molding, for instance, into
bottles, toys, food containers and plastic bags, while PVC finds use in buildings
and construction (450% of all PVC), automotive industry, and medical
devices. The prominent resistance to degradation of PVC is the reason why it is
often preferred in long-life applications such as outdoor tubes and floor
coverings.
176 Chapter 6
Figure 6.8 Images of surfaces of an A-type sample for 0.5% (a) and 5% (b) strain
deformations, and for 5% strain deformations in a B-type sample (c).
The multilayer structure consisted of a polyurethane protective layer over the

substrate and two layers of TiO2 on the protective layer, deposited by spin-
coating of a Degussa P25 suspension. Finally, immobilized TiO2 particles
bound in a diluted polyurethane dispersion were applied to fix the underlying
particles and improve the mechanical resistance of the TiO2 layer. To obtain
photocatalytically active materials reactive oxygen-plasma surface etching of
the fabricated coatings was performed. In the absence of this final treatment,
the reactivity of such films was either very low or absent. This treatment, kept
quite short (15 s), gave rise to etching of only polyurethane binder on the outer
surface in order to expose a higher amount of TiO2 particles to the reaction
ambient.
The so-obtained samples (Figure 6.9) were characterized by SEM. It can be
seen that the plasma treatment promotes a high exposure of TiO2 particles and
a prominent porosity of sample surfaces. Extending the plasma treatment over
a certain time does not result in a higher photocatalytic degradation rate,
probably because light can only penetrate through a limited film thickness.
TiO2
Protective layer (PU)

PVC
+PU binder
PU binding layer
TiO2 TiO 2
TiO2
Protective layer (PU)

PVC
Figure 6.9 Scheme of multilayer films deposited on PVC (PU stands for
polyurethane).
Figure 6.10 Chemical reaction leading to surface modification of nanoparticulate

titanium dioxide. (Reproduced with permission from ref. 11.)
Samples were tested in the degradation of palmitic acid in the gas phase under
UV irradiation. HDPE samples exhibited a higher activity than PVC ones,
which can be related to photocatalytic inhibition caused by PVC plasticizers.
Nanostructured titanium dioxide, modified on its surface with silanes con-
taining organic or fluoro-organic side chains, constitutes a smart transparent
coating applicable on the surface of plastics.11
The coating can be obtained starting from a TiO2 anatase sol (obtained
through the hydrolysis of titanium tetraisopropoxide by a conventional
method); further drying of the powder by rotovapor, dispersion in toluene,
followed by mixing with a fluorosilicate and centrifugation to separate the
particle agglomerates affords a fluorosilane-modified TiO2 with moderate
polarity (Figure 6.10). These particles are then added to a binding sol (made of
pre-hydrolyzed methyl-silica) in methyl ethyl ketone. The coating can be
applied on PVC through spray, dip, spin or flow coating. The best performing
thickness of the resulting film was 1–2 mm. It should be underlined that the
transparency of the coating is guaranteed only if the particle size of the anatase
is significantly below 20 nm (since TiO2 has a refractive index of ca. 2.5).
Accordingly the so-prepared sol affords particle sizes of 5–10 nm.
Interestingly, while coating-sols containing modified TiO2 nanoparticles
look completely homogenous, after application of the coating sol and sub-
sequent evaporation of the solvents from a wet film a gradual change of the
178 Chapter 6
Figure 6.11 Modified TiO2 nanocoating before and after activation. (Adapted with
balance between polar and nonpolar compounds in the film take place that,
finally, leads to a thermodynamically driven diffusion of TiO2 nanoparticles
towards the interface between coating and air.
During the first hours of UV irradiation, film activation takes place, in which
the organic side chains at the surface of the TiO2 particles are oxidized,
revealing the active form of the particles. During activation the contact angle is
reduced from 90–1001 to below 101, i.e., to superhydrophilic behavior. This
leads to the formation of a SiO2 protective layer between the polymeric sub-
strate and the catalyst (Figure 6.11).
6.2 Photocatalytic Textiles

Having clothes coated with a thin transparent layer of TiO2 can give major
added value, by decomposing the organic matter deposited on the textiles. The
smell of smoke on smokers’ clothes can also be eliminated, along with patho-
gens, such as bacteria, that under normal conditions can survive on textile
surfaces for up to three months. Self-cleaning textiles could be generally applied
also for sportswear, military uniforms and carpets (indoors and outdoors).12
Coating cotton is quite easy, whereas fibers like wool, silk and hemp have
proved less amenable. These fibers, indeed, are made of a protein called keratin,
which does not have any reactive chemical groups on its surface to bind with
TiO2; consequently, their surface should be modified to establish a chemical
bond with TiO2.
Thus, a dispersion of Degussa P25 particles and polyglycol in water can be
padded on cotton woven fabrics, by using a reactive amino-silicone additive for
padding TiO2 particles on the fabrics.13 The cotton has to be previously treated
in a boiling bath containing sodium carbonate and soap. Afterwards the fabric
samples were padded twice with a treatment solution on a laboratory padding
mangle.
Another way to support TiO2 on cotton is a simple coating process. In this
way mixing TiO2 with self-crosslinking acrylic binders yields a coating for-
mulation that can be applied after treating the textile with a water repellent
agent.
Figure 6.12 shows SEM images of untreated (a), TiO2-padded (b) and TiO2-
coated cotton (c) fabrics. The structure of cotton fiber is a typical round and
smooth surface. The morphological change in the appearance of cotton fiber
after TiO2-padding can be clearly seen in Figure 6.12(b). The cotton fiber
surface is covered with TiO2 particles, becoming rough and uneven. The
loading of TiO2 on cotton fibers was, thereby, proved, although their
Figure 6.12 SEM images of untreated (a), TiO2-padded (b) and TiO2-coated (c)
cotton fabrics. (Reproduced with permission from ref. 13.)
180 Chapter 6
distribution on the fiber surface was not quite even, probably owing to
aggregation of some fine TiO2 particles. The morphological features of TiO2-
coated cotton fabric surface differ greatly from those of the TiO2-padded
cotton fabric, with few TiO2 particles since they probably aggregate with the
binder layer.
Gaseous ammonia decomposition was proven to take place by using these
materials. Both padded and coated fibers were active, but in the former case the
TiO2 loading had a primary influence on reaction rate, probably because of the
much greater exposed surface than in the coated material. Hence, the padded
textile was ca. 2.5-fold more effective than the coated one, in terms of kinetic
constants. On the other hand, the TiO2-coated cotton fabric showed relatively
strong adsorption of ammonia molecules due to the presence of the acrylic
binder layer partially covering TiO2 particles on the surface.
Sol-gel methods at low temperature (o100 1C) can be surely applied in the
preparation of TiO2-modified cotton.14 Cellulose fibers, previously cleaned
with acetone, can be covered by using a titanium isopropoxide (TIP) sol, pre-
pared through mixing with isopropanol and triethylamine as stabilizer of the
solution. The addition of an acidic aqueous solution then yields a TiO2
transparent sol, with which the cellulose fibers can be impregnated. After
drying, a boiling treatment in water can remove all the unattached TiO2 par-
ticles from the surface of the fibers.
SEM images of such materials (Figure 6.13) show how the folds running
parallel to the elongation direction, present in the pure fibers, are covered by a
continuous and homogeneous TiO2 thin film, which obscures the surface folds
below. The formation of some aggregates is also clearly visible. The presence of
a badly crystallized anatase phase was shown by X-ray diffraction.
Accordingly these TiO2-covered cellulose fibers show high photocatalytic
efficiency in decomposing adsorbed Methylene Blue and heptane-extracted
bitumen fraction under solar-like light. Furthermore, the TiO2 film, although
highly efficient in pollutant degradation, does not promote simultaneous fiber
degradation.
A metal doping agent, such as gold, can be introduced in the above pre-
paration by soaking in a HAuCl4 aqueous solution with subsequent irradiation
to promote reduction of Au cations, thus yielding Au nanoparticles on a TiO2
film.14b The resulting cotton fibers are, hence, covered by a thin Au/TiO2 film
consisting of anatase nanocrystallites that strongly adhere to the support, with
a purple color and a significantly improved photocatalytic activity under solar
light with respect to undoped samples.
Fibrous proteins, such as keratins, which are also the main structural con-
stituents of animal tissues, are present for instance in wool, silk, hemp and
spider silk. Self-cleaning keratin fibers can be realized following a bottom-up
nanotechnology approach in which anatase nanocrystals of TiO2 are prepared
and carefully applied to the fibers via a low temperature sol-gel process to
maintain their intrinsic properties, which would be drastically affected by
warming at high temperature. The sol-gel process consists of a procedure
similar to the previously described ones, based on titanium tetraisopropoxide
TiO2 on Plastic, Textile, Metal and Paper
181
Figure 6.13 SEM images of pure cellulose fiber (a, b), and TiO2-impregnated fiber (c, d). (Reproduced with permission from ref. 14a.)
182 Chapter 6
Figure 6.14 Red wine stain degradation on pristine keratin fibers (PO) and on two
TiO2-modified fibers (TO and TS) under UV irradiation. (Reproduced
hydrolysis. The functionalization confers both self-cleaning properties and self-

protection against UV degradation.15 Exposure of such proteins to UV-light
indeed would normally result in a major change in their physicochemical and
hence mechanical properties. The photocatalytic self-cleaning properties of the
prepared samples were investigated by the decomposition of Methylene Blue
and degradation of food stains. Figure 6.14 shows the degradation of red wine
stains under UV irradiation in the case of pristine and TiO2-modified fibers. TS
in Figure 6.14 indicates a sample treated by succinylation before deposition of
TiO2. This treatment allows for an increased presence of TiO2 on the surface
and hence a higher photocatalytic activity, since succinic anhydride can
introduce additional carboxylic groups by acylation, resulting in enhanced
bonding between TiO2 and the fibers (Figure 6.15). Interestingly, the described
method allows us to obtain many self-cleaning textiles, such as wool.
Electrospun polymeric nanofibers with high photocatalytic activity can be
prepared by absorption of negatively charged colloidal TiO2 nanoparticles
applying a layer-by-layer (LbL) deposition with positively charged polyhedral
oligosilsesquioxane (POSS) molecules. Application fields of this method are
protective clothing systems, photocatalysis, sensors and electrodes.16 Electro-
spinning is a popular method for obtaining ultrafine fibers with micrometer
diameters from various polymer solutions or melts, whereas the LbL assembly
process involves sequential adsorption of oppositely charged species, resulting
Figure 6.15 Succinylation of keratins and the binding action of TiO2 to the modified
agent. (Reproduced with permission from ref. 15.)
POSS
Plasma POSS TiO2 TiO2
Figure 6.16 Scheme of electrospinning process followed by LbL TiO2 deposition.
in the deposition of a thin, uniform film. Electrospinning of nanofibers from

polystyrene, polyacrylonitrile, blends of poly(methyl methacrylate) (PMMA)
and poly(ethylene oxide) (PEO), and poly(dimethylsiloxane-b-ether-imide)
(PSEI) can be carried out, followed by a LbL assembly, showing that the
method is of general interest in depositing TiO2.
Figure 6.16 shows the scheme of the electrospinning preparation method. In
practice a distribution of fiber diameters is obtained (400–1300 nm), along with
a random orientation of the fibers. This is typical of electrospun polymers. The
layer thickness of particles on the fiber is approximately 25 nm. Photocatalytic
abatement of the toxic allyl alcohol (2-propen-1-ol) in vapor phase can be
carried out with satisfactory results.
Lyocell fibers, produced from wood pulp cellulose, can be functionalized by
TiO2 through two different methods.17 TiO2 nanoparticles can be (i) used and
bound by a SiO2 nanocoating on the fiber surface or (ii) produced directly on
the fiber surface by a sol-gel procedure similar to that previously analyzed. Red
beet sap and red wine were used to test the self-cleaning properties of the
resulting materials. Samples prepared in both ways demonstrated photo-
catalytic activity, even though a higher degradation of organics was observed
when using TiO2–SiO2 nanocoating compared to TiO2 coating. Clearly, the
184 Chapter 6
longer the treated fabric was exposed to daylight the more intensive was the
change in the stain. Table 6.1 shows that the most relevant changes are those
corresponding to bending, compression and surface properties, whilst the
changes in tensile and shear properties are smaller. The coatings on the fibers
moreover reduce the shear rigidity (indicated by G) slightly. In addition, a
greater decrease in hysteresis of the shear force at 0.51 (2HG) and 51 (2HG5) is
present. The low shear hysteresis (2HG) has an advantageous influence on
handle and indicates a greater softness of the fabric, whereas the value of
(2HG5) influences the fabric fitting and appearance of the garment or similar
3D textile products. Generally speaking it is possible to state that nanocoating
influences not only surface morphology but also the mechanical properties of
the presented textiles. The greatest influence of nanocoatings results in changes
in the fabrics’ bending, compression and surface properties. By using a TiO2–
SiO2 composite nanocoating an increase in fabric flexibility and soft feeling, as
well as fullness and softness, is perceived, while TiO2 nanocoating slightly
reduces these hand characteristics.
6.3 Photocatalytic Paper

Among the physical properties of a paper, its visible appearance is very
important, especially to the printer and to the final reader. For this reason,
there have been many efforts to produce paper at high whiteness levels. Incident
light can be transmitted, scattered, reflected or absorbed and all these phe-
nomena may occur separately or in combination. A paper sheet appears
completely white if it totally reflects light, and scatters diffusively at all wave-
lengths of the visible spectrum.
TiO2 is usually used in paper products to improve opacity and whiteness.
However, its higher cost compared to clay and calcium carbonate limits con-
ventional its usage to high-added-value printing papers.
The field of photocatalytic paper, including the study of its related
mechanisms and technologic development, is in its early stages. Few patents
and research have been reported. The main applications described are the
destruction of organic molecules and sterilization.18
A key point is the investigation of methods to fix TiO2 to cellulose substrates
to minimize photochemical damage to the paper. Another approach is based on
the use of (i) zeolites, to give higher surface areas and hence enhanced miner-
alization, and (ii) metal-doping for enhanced photocatalytic disinfection.
The first article reporting a paper with photocatalytic properties was by
Matsubara et al. in 1995, wherein the authors described the catalytic destruc-
tion of acetaldehyde in the vapor phase with photocatalytic paper and weak
fluorescent light illumination.19
There are two main approaches for adding a photocatalyst to paper in
conventional papermaking: wet-end addition, where the TiO2 is deposited onto
individual fibers before sheet formation (i.e., the filtration step), and size press
treatment, where the dry paper sheet is impregnated with a photocatalyst.20
Table 6.1 Low-stress mechanical properties of pristine lyocell (sample 1), modified lyocell through TiO2 particle/SiO2 method
(sample 2), modified lyocell through TiO2 using a sol-gel method. (Reproduced with permission from ref. 17.)
Properties Symbols and units Typical values Sample 1 Sample 2 Sample 3
Tensile properties
Tensile energy WT [N/m] 5–20 5.95 5.25 ( 11.8%) 5.69 ( 4.4 %)
Tensile resilience RT 55–70 51.98 57.70 ( þ 11.0%) 54.60 ( þ 5.0%)
Linearity LT [-] 0.55–0.70 0.543 0.522 ( 3.9%) 0.554 ( þ 2.0%)
Extensibility (warp) EMI [%] 3–5 3.03 3.00 ( 1.0%) 2.88 ( 5.1 %)
(weft) EM2 [%] More than 4 5.71 5.20 ( 8.9 %) 5.49 ( 3.9%)
Shear properties
Shear rigidity (warp) Gl [N/(m-11)] 0.6–0.9 0.37 0.34 ( 8.1 %) 0.37 (0.0 %)
(weft) G2[N/(m-l1)] 0.6–0.9 0.34 0.33 ( 2.9 %) 0.33 ( 2.9 %)
Shear stress at 0.51 2HG [N/m] 0.42 0.27 ( 35.7 %) 0.32 ( 23.8%)
TiO2 on Plastic, Textile, Metal and Paper
Shear stress at 51 2HG5 [N/m] 1–3 1.41 1.03 ( 27.0 %) 1.07 ( 24.1 %)
Bending properties
Bending rigidity (warp) BI [x[04 N-m] 0.04–0.10 0.090 0.059 ( 34.4 %) 0.075 ( 16.6%)
(weft) B2 [xl04 N-m] 0.04–0.10 0.052 0.042 ( 19.2%) 0.059 ( þ 13.5%)
Bending moment 2HB[xl02N] 0.015–0.50 0.043 0.014 ( 67.4 %) 0.024 ( 44.2 %)
Compression properties
Compression energy WC [N/m] 0.1–0.5 0.135 0.135 (0.0 %) 0.101 ( 25.2 %)
Compression resilience RC [%] 35–60 40.85 47.29 ( þ 15.8%) 51.37 ( þ 25.8 %)
Linearity LC[-] 0.265 0.301 ( þ 13.6%) 0.337 ( þ 27.2 %)
Fabric thickness at 49 N/m2 To [mm] 0.332 0.396 ( þ 19.3 %) 0.270 ( 18.7%)
Fabric thickness at 4900 N/m2 Tm [mm] 0.130 0.216 ( þ 66.2 %) 0.150 ( þ 15.4%)
Surface properties
Coefficient of friction MIU [-] 0.15–0.30 0.173 0.351 ( þ 202.9 %) 0.280 ( þ 61.9%)
Mean deviation of MIU MMD [-] 0.010–0.05 0.0121 0.0148 ( þ 22.3 %) 0.0157 ( þ 29.8 %)
Geometrical roughness SMD [mm] 2–15 2.855 3.421 ( þ 19.8%) 3.298 ( þ 15.5%)
185
186 Chapter 6
Though ensuring a complete distribution of TiO2 throughout the sheet, the
major challenge of wet-end addition of TiO2 is the retention of nanometer-
scale, anionic and stable colloidal TiO2 particles in the paper sheet during the
rapid filtration process on a paper machine. The implementation of high
molecular weight cationic water-soluble polymers make, on the one hand, the
TiO2 particles deposit on the wood fibers before paper sheet formation, while,
on the other hand, they can also cause the TiO2 particles to flocculate with
themselves and with other fillers, giving rise to the formation of large aggre-
gates (5 mm). Owing to the covering effect of the cationic polymers the paper
surfaces are likely to have a lower TiO2 content than the inner part of the sheet.
Wet-end addition can be performed though by synthesizing TiO2 particles in
the presence of fibers, heating to only 97 1C, via titanium tetraisopropoxide
hydrolysis.20
In size press treatment, dry paper is impregnated with TiO2 by passing it
through a size press where the paper surface is exposed to an aqueous sus-
pension of TiO2 and a binder, typically starch.
The papermaker can control the extent of penetration of the size press dis-
persion into the paper, by varying the base paper hydrophobicity and porosity.
This process allows for TiO2 concentration near the paper surfaces; because
TiO2 is coated with a binder, the local environment around the TiO2, along
with porosity and hydrophobicity extents, can be strictly controlled and dif-
ferentiated from the untreated regions of the paper sheet.21
The presence of TiO2 can be responsible for major photodegradation of
paper compared with TiO2-free papers. Methods to protect cellulose have been
reported and are based on the co-precipitation of TiO2 with colloidal silica,21a
aluminium silicates or polymeric binders.22
Although information on paper composition and the influence of structure
on photocatalytic activity has not been completely clarified, it is known that
lignin works as photosensitizer and thus could perhaps be used to enhance TiO2
efficiency.23
Photoresistant non-woven paper, produced by the company Ahlstrom21 by
using TiO2 Degussa P25 and Millennium PC500, has used to degrade diuron in
aqueous solution.24 This flexible photocatalytic paper is prepared by using
colloidal silica as binder. Figure 6.17 reports the experimental set-ups used to
analyze TiO2 supported both on paper and in slurries; for comparison purposes
the same amount of TiO2 was employed in each case. The reaction mixtures
were irradiated by means of a 125W UV-lamp in both cases.
The nature of the TiO2 particles (P25 or PC500) deposited on Ahlstrom
paper NW10 does not seem to influence the kinetics of the photocatalytic
degradation of diuron, in contrast to results obtained with suspended powders
(Figure 6.18). The efficiency of C500 deposited on paper is, however, very close
to that obtained with unsupported PC500. The difference in shape between the
two disappearance curves in the first tens of minutes of degradation could be
caused by additional diuron adsorption in the dark on the paper and on the
silica binder. Conversely, P25/NW10 presents an efficiency that is two times
lower than that of P25 powder. These differences in behavior for P25 and
Figure 6.17 Photoreactor scheme used to test the activity of TiO2 supported on paper
(a) and of the corresponding slurries for comparison (b). (Reproduced
PC500 supported on NW10 could be explained by the better dispersion of

PC500 on NW10 due to its smaller particle size.
6.4 TiO2 on Metals

Metals such as stainless steel, aluminium alloy and copper alloy, widely
employed in household, construction and industrial contexts, can be functio-
nalized by means of TiO2 to gain specific properties, such as photocatalytic
activity, surface superhydrophilicity and antibacterial activity. A protective
effect against corrosion can be achieved at the same time by uniformly covering
metals with TiO2 films.25
Thick TiO2 films can be prepared by integrating the preparation of a sol from
titanium tetraisopropoxide hydrolysis in the presence of diethanolamine along
with its mixing with Degussa P25 TiO2 particles. Films obtained from the
modified sol-gel are about ten times thicker for a single dip coating/heat
188 Chapter 6
Figure 6.18 Photodegradation of diuron. Comparison of the efficiencies of P25 (a)

and PC500 (b) in powder and supported on NW10 paper. (Reproduced
treatment cycle than films obtained from the sol without powder addition. The
prepared thick films were smooth and free of macrocracking and fracture. The
aggregate size of these films was in the range 100–150 nm and films containing
both anatase and rutile phases can be obtained. Moreover, the so-prepared
films are much harder than films obtained from unmodified sols, and displayed
excellent adhesion to the substrate.26 These catalysts were found to be photo-
catalytically active in the degradation of 4-chlorobenzoic acid.
An efficient nanoparticle deposition system (NPDS) applicable to metal
surfaces consists in spraying nano- and micro-sized TiO2 powders through a
supersonic nozzle at room temperature under low vacuum conditions.27 The
accelerated particles can be thus deposited on many substrates without thermal
treatments. Figure 6.19 shows the components of an NPDS, including the air
compressor, powder supplier, vacuum chamber, vacuum pump and controllers.
The nozzle accelerates particles to a supersonic flow, which then impacts
against the substrate. Commercial rutile TiO2 powder was used to apply TiO2
coatings on stainless steel (Figure 6.20) and on polymeric substrates with a
thickness of ca. 300 nm. The TiO2-covered stainless steel showed hardness and
modulus values ca. 10% higher than the uncovered ones. This method was
found to be applicable also to Al and Cu alloys.
A uniform and active TiO2 film can be coated on stainless steel substrates by
using a microemulsion of an organic surfactant (Triton X-100) in cyclohexane–
water solvents mixed with titanium isopropoxide. Finally, the TiO2 sol (con-
tained in water droplets) can be deposited by dip-coating.
Figure 6.19 Scheme of a nanoparticle deposition system. (Reproduced with permis-

sion from ref. 27.)
Figure 6.20 Images of a 5 5 mm TiO2 coating on stainless steel: (a) optical image
and (b) SEM image. (Reproduced with permission from ref. 27.)
190 Chapter 6
Calcination at 500 1C to both remove organics and crystallize TiO2
completes the procedure.28 Increasing amounts of Fe(II) and Fe(III) ions
diffuse from the stainless-steel substrate to TiO2 films with increasing calcina-
tion time.
The films were superhydrophilic. Water contact angles for freshly prepared
anatase TiO2 films on stainless steel were indeed about 15–201 due to the
Figure 6.21 (a) Contact angle of TiO2 films coated on stainless steel with different
calcination times versus UV illumination time (540 mW cm2, 22 1C, RH
80%, in air); (b) change in water contact angles versus storage time in
the dark under ambient conditions. (Reproduced with permission from
ref. 28.)
presence of some surface defects. However, when these samples were kept in the
dark, the water contact angles increased to 50–601. To turn these slightly
hydrophilic films into photo-induced hydrophilic ones, they were illuminated
with a UV lamp under normal conditions. Figure 6.21(a) shows that water
contact angles sharply decrease from 45–501 to 10–181 within 60 min and then
gradually decrease to 2–81 after 300 min irradiation. Keeping the same films in
the dark for 20–30 days results in the re-establishment of the previous
Figure 6.22 TiO2-treated plastic films are stain-proof and can be cleaned easily with
plain water. (Photograph courtesy of Nippon Soda Corporation.)
Figure 6.23 A photocatalytic tarpaulin storage tent is easily cleaned by rainwater.

(Photograph courtesy of Nippon Soda Corporation.)
192 Chapter 6
conditions (see Figure 6.21b). This behavior could be ascribed to the fact that
the surface defective sites can be healed or replaced gradually by oxygen atoms,
which causes the highly hydrophilic surface to be converted into a slightly
hydrophilic one.
In addition, these films were tested as antibacterial devices for the steriliza-
tion of Bacillus pumilus. The efficiency found was remarkably higher than that
without TiO2 films; UV light alone did not cause sterilization. Moreover, in the
absence of UV illumination the survival ratio was not reduced, so that one can
conclude that the films itself was not toxic to Bacillus pumilus. Thus the bac-
tericidal effect was due to the photocatalytic reaction of the TiO2 films.
6.5 Practical Applications

Commercial examples of polymeric materials are still few and not as wide-
spread as for glass, cement or ceramics. However, the field of photocatalytic
plastics has been deeply explored, yielding interesting results, such those of the
Nippon Soda Corporation (Figure 6.22). The transparent stain-proof plastic
film is ideal for objects exposed to oily pollutants such as those present in the
kitchens.29
The same company produced a storage tent (Figure 6.23) made of TiO2-
modified tarpaulin material, which has remained clean for many years, being
washed only by rainwater.
Other polymeric photocatalytic materials have been produced by Sekisui
Jushi Corporation for application as road signals and soundproof barriers
(Figure 6.24). These products remain clean and are able to degrade the
deposited smog.30
Commercial TiO2-coated PVC has been developed by Taiyo Kogyo Cor-
poration in collaboration with Nippon Soda Co. (Figure 6.25). PTFE (poly-
tetrafluoroethylene) was also made photocatalytic by mixing the photocatalyst
material with resin in the top surface layer of the PTFE, since direct coating of
the photocatalyst to PTFE was found to be very difficult due to the differences
Figure 6.24 TiO2-treated polycarbonate for application in road signals and sound-
proof road barriers. (Photograph courtesy of Sekisui Jushi Corporation.)
Figure 6.25 Two examples of TiO2-coated PVC: (left-hand side) an ecology museum
in Taiwan; (right-hand side) an external chapel in Osaka. (Photograph
courtesy of Taiyo Kogyo Corporation.)
Figure 6.26 Scheme of the four photocatalytic products proposed by Taiyo Kogyo.
(Photograph courtesy of Taiyo Kogyo Corporation.)
in physicochemical properties. An experiment carried out by the two companies

has shown that 10 000 m2 of photocatalyst-coated fabric decomposes the major
air pollutant nitrogen dioxide (NO2) expelled by 1.7 four-ton trucks.
Recently (2008) the same company presented a new product line, which
consists of a photocatalytic membrane, in four types: ‘‘Ever Fine Coat,’’ ‘‘Sky
Clear Coat,’’ ‘‘Sky See-Through’’ and ‘‘Self-Max’’.31 The first product is based
on PTFE, where as the other three products are based on PVC. ‘‘Ever Fine
Coat,’’ in particular, is available in different colors (white, gray, ivory, blue,
194 Chapter 6
Figure 6.27 Photographs and SEM image of fibers for textiles by Kuraray Trading
Co. (Photograph courtesy of Kuraray Trading Co.)
Figure 6.28 Self-cleaning and self-sterilizing paper applied in window blinds and in
dresses. (Photograph courtesy of MOLZA Corporation.)
Figure 6.29 An aluminium-siding coated with TiO2. (Photograph courtesy of YKK

Corporation.)
etc.) and has superb self-cleaning performances. The other products are white,
except for ‘‘Sky See-Through’’ that shows a high transmittance (ca. 65%).
Figure 6.26 shows the structure of these membranes.
Kuraray Trading Co., experts in polyester filament manufacture, has
developed unique polymer products such as an antibacterial deodorizing fiber
and the ethylene vinyl alcohol-based ‘‘Sophista.’’ These products were the
results of extensive and original development of composite materials incor-
porating Kuraray polyester and other fibers, along with secondary products.32
Figure 6.27 shows some pictures of the self-cleaning textiles developed and a
SEM image of the fiber used to manufacture them.
Even in the case of photocatalytic paper materials, the examples are
very few and mainly by Japanese companies. Ahlstrom started working on
photocatalytic nonwoven products in 1996, describing them in conferences
and to the press and now they propose these products as efficient devices with
which to purify air and water.33 Nippon Paper (Tokyo, Japan), on one other
hand, developed a few years ago the ‘‘Light Catalytic Newsprint’’ (PDASHt)
with Yomiuri, one of Japan’s largest newspaper publishers.34 These newsprints
(containing TiO2) deodorize the surrounding air when irradiated by UV and
ambient light. The Japan Synthetic Textile Inspection Institute Foundation
confirmed that PDASHt successfully led to a reduction of more than 99% in
the concentration of acetaldehyde, i.e., the main component of cigarette
odors, in ca. 20 h. Moreover, the developed technology allows for the
196 Chapter 6
production of coated paper that is compatible with any type of printing
machine in high-speed printing. The virgin pulp source to produce this paper is
made from PEFCC (Pan-European Forest Certification Council) certified
woodchips.
Figure 6.28 shows other commercial products produced from photocatalytic
paper by the MOLZA Corporation.35 Finally, Figure 6.29 shows an alumi-
nium-siding coated with TiO2 by the YKK Corporation, in a building
constructed in 1999 in Sendai.36
References
1. A. Fujishima, X. Zhang and D. A. Tryk, TiO2 photocatalysis and related
2. (a) M. P. Paschoalino, J. Kiwi and W. F. Jardim, Gas-phase photocatalytic
decontamination using polymer supported TiO2, Appl. Catal. B: Environ.,
2006, 68, 68–73; (b) K. O. Awitor, A. Rivaton, J.-L- Gardette, A. J. Down
and M. B. Johnson, Photo-protection and photo-catalytic activity of
crystalline anatase titanium dioxide sputter-coated on polymer films, Thin
Solid Films, 2008, 516, 2286–2291; (c) A. Kubacka, M. Ferrer, M. L.
Cerrada, C. Serrano, M. Sánchez-Chaves, M. Fernández-Garcı́a, A. de
Andrés, R. J. Jiménez Riobóo, F. Fernández-Martı́n and M. Fernández-
Garcı́a, Boosting TiO2-anatase antimicrobial activity: Polymer-oxide thin
films, Appl. Catal. B: Environ., 2009, 89, 441–447.
3. M. Birnie, M. Gillott and S. Riffat, The immobilization of titanium dioxide
on organic polymers, for a cost effective and energy efficient means of
improving indoor air quality, Int. J. Green Energy, 2006, 3, 101–114.
4. J.-H. Yang, Y.-S. Han and J.-H. Choy, TiO2 thin-films on polymer
substrates and their photocatalytic activity, Thin Solid Films, 2006, 495,
266–271.
5. M. Langlet, A. Kim, M. Audier and J. M. Hermann, Sol-gel preparation of
photocatalytic TiO2 films on polymer substrates, J. Sol-Gel Sci. Technol.,
2002, 25, 223–234.
6. M. S. Vohra and K. Tanaka, Enhanced photocatalytic activity of Nafion-
coated TiO2, Environ. Sci. Technol., 2001, 35, 411–415.
7. Y. Zhiyong, D. Laub, M. Bensimon and J. Kiwi, Flexible polymer TiO2
modified film photocatalysts active in the photodegradation of azo-dyes in
solution, Inorg. Chem. Acta, 2008, 361, 589–594.
8. J. O. Carneiro, V. Teixeira, A. Portinha, A. Magalhães, P. Coutinho, C. J.
Tavares and R. Newton, Iron-doped photocatalytic TiO2 sputtered coat-
ings on plastics for self-cleaning applications, Mater. Sci. Eng., 2007, 138,
144–150.
9. C. J. Tavares, S. M. Marques, S. Lanceros-Méndez, V. Sencadas, V.
Teixeira, J. O. Carneiro, A. J. Martins and A. J. Fernandes, Strain analysis
of photocatalytic TiO2 thin films on polymer substrates, Thin Solid Films,
2008, 516, 1434–1438.
10. J. Kasanen, M. Suvanto and T. T. Pakkanen, Self-cleaning, titanium
dioxide based, multilayer coating fabricated on polymer and glass surfaces,
J. Appl. Polym. Sci., 2009, 111, 2597–2606.
11. H. Schmidt, M. Naumann, T. S. Müller and M. Akarsu, Application of
spray techniques for new photocatalytic gradient coatings on plastics, Thin
Solid Films, 2006, 502, 132–137.
12. (a) K. Sunada, Y. Kikuchi, K. Hashimoto and A. Fujishima, Bactericidal
and detoxification effects of TiO2 thin film photocatalysts, Environ. Sci.
Technol., 1998, 32, 726–728; (b) K. Qi, W. A. Daoud, J. H. Xin, C. L.
Mak, W. Tang and W. P. Cheung, Self-cleaning cotton, J. Mater. Chem.,
16, 4567–4574.
13. Y. Dong, Z. Bai, R. Liu and T. Zhu, Decomposition of indoor ammonia
with TiO2-loaded cotton woven fabrics prepared by different textile fin-
ishing methods, Atmos. Environ., 2007, 41, 3182–3192.
14. (a) M. J. Uddin, F. Cesano, F. Bonino, S. Bordiga, G. Spoto, D. Scarano
and A. Zecchina, Photoactive TiO2 films on cellulose fibres: synthesis and
characterization, J. Photochem. Photobiol. A: Chem., 2007, 189, 286–
294; (b) M. J. Uddin, F. Cesano, D. Scarano, F. Bonino, G. Agostini, G.
Spoto, S. Bordiga and A. Zecchina, Cotton textile fibres coated by Au/
TiO2 films: synthesis, characterization and self cleaning properties, J.
Photochem. Photobiol. A: Chem., 2008, 199, 64.
15. W. A. Daoud, S. K. Leung, W. S. Tung, J. H. Xin, K. Cheuk and K. Qi,
Self-cleaning keratins, Chem. Mater., 2008, 20, 1242–1244.
16. J. A. Lee, K. C. Krogman, M. Ma, R. M. Hill, P. T. Hammond and G. C.
Rutledge, Highly reactive multilayer-assembled TiO2 coating on electro-
spun polymer nanofibers, Adv. Mater., 2009, 21, 1252–1256.
17. N. Veronovski, A. Rudolf, M. S. Smole, T. Kreze and J. Geršak, Self-
cleaning and handle properties of TiO2-modified textiles, Fibers Polym.,
2009, 10, 551–556.
18. (a) R. Pelton, X. Geng and M. Brook, Photocatalytic paper from colloidal
TiO2-fact or fantasy, Adv. Colloid Interface Sci., 2006, 127, 43–53; (b) L.
Ye, C. D. M. Filipe, M. Kavoosi, C. A. Haynes, R. Pelton and M. A.
Brook, Immobilization of TiO2 nanoparticles onto paper modification
through bioconjugation, J. Mater. Chem., 2009, 19, 2189–2198.
19. H. Matsubara, M. Takada, S. Koyama, K. Hashimoto and A. Fujishima,
Photoactive TiO2 containing paper: preparation and its photocatalytic
activity under weak UV light illumination, Chem. Lett., 1995, 767–768.
20. W. A. Daoud, J. H. Xin and Y.-H. Zhang, Surface functionalization of
cellulose fibers with titanium dioxide nanoparticles and their combined
bactericidal activities, Surf. Sci., 2005, 599, 69–75.
21. (a) P. Escaffre, P. Girard, J. Dussaud and L. Bouvier, Photocatalytic
composition having binding agent containing colloidal silica, 1999, Pat.
Appl. WO99-FR748 9951345; (b) A. Aguedach, S. Brosillon, J. Morvan
and E. K. Lhadi, Photocatalytic degradation of azo-dyes reactive black 5
and reactive yellow 145 in water over a newly deposited titanium dioxide,
Appl. Catal. B: Environ., 2005, 57, 55–62.
198 Chapter 6
22. N. Kimura, S. Abe, T. Yoshimoto and S. Fukayama, Photocatalyst-car-
rying structure and photocatalyst coating material, 2001, US Pat. 6228480
B1.
23. L. R. C. Barclay, M.-C. Basque and M. R. Vinqvist, Singlet-oxygen
reactions sensitized on solid surfaces of lignin or titanium dioxide: product
studies from hindered secondary amines and from lipid peroxidation, Can.
J. Chem., 2003, 81, 457–467.
24. M. El Madani, C. Guillard, N. Pérol, J. M. Chovelon, M. El Azzouzi, A.
Zrineh and J. M. Herrmann, Photocatalytic degradation of diuron in
aqueous solution in presence of two industrial titania catalysts, either as
suspended powders or deposited on flexible industrial photoresistant
papers, Appl. Catal. B: Environ., 2006, 65, 70–76.
25. (a) Y. Zhu, L. Zhang, L. Wang, Y. Fu and L. Cao, The preparation and
chemical structure of TiO2 film photocatalysts supported on stainless steel
substrates via the sol-gel method, J. Mater. Chem., 2001, 11, 1864–
1868;23.(b) P. Evans and D. W. Sheel, Photoactive and antibacterial TiO2
thin films on stainless steel, Surf. Coat. Technol., 2007, 201, 9319–9324.
26. (a) G. Balasubramanian, D. D. Dionysiou, M. T. Suidan, V. Subramanian,
I. Baudin and J.-M. Laı̂né, Titania powder modified sol-gel process for
photocatalytic applications, J. Mater. Sci, 2003, 38, 823–831; (b) G.
Balasubramanian, D. D. Dionysiou, M. T. Suidan, I. Baudin and J.-M.
Laı̂né, Evaluating the activities of immobilized TiO2 powder films for the
photocatalytic degradation of organic contaminants in water, Appl. Catal.
B: Environ., 2004, 47, 73–84.
27. D. M. Chun, M. H. Kim, J. C. Lee and S. H. Ahn, TiO2 coating on metal
and polymer substrates by nano-particle deposition system (NPDS), CIRP
Ann.-Manuf. Technol., 2008, 57, 551–554.
28. J. C. Yu, W. Ho, J. Lin, H. Yip and P. K. Wong, Photocatalytic activity,
antibacterial effect, and photoinduced hydrophilicity of TiO2 films coated
on a stainless steel substrate, Environ. Sci. Technol., 2003, 37, 2296–2301.
29. Nippon Soda Corporation: http://www.nippon-soda.co.jp
30. Sekisui Jushi Corporation : http://www.jislon.com/contents/top/top.html.
31. Details of products from Taiyo Kogyo Corporation are available online at
http://www.makmax.com/business/tio2_fabric.html
32. Details of photocatalytic products from Kuraray Trading Co. are available
online at http://www.kuraray.co.jp/en/release/2003/031219.html
33. Details of photocatalytic paper produced by Ahlstrom can be found online
at http://www.ahlstrom.com
34. Details about photocatalytic paper produced by Nippon Paper can be
found online at http://www-japan.org/trends/07_sci-tech/sci080131.html
35. Details about photocatalytic paper produced by Molza Corporation can be
found online at http://www.molza.co.jp
36. Details about photocatalytic paper produced by YKK Corporation can be
found online at http://www.ykk.com
CHAPTER 7
Devices for Water and Air

Purification
7.1 Devices for Water Purification
Photocatalytic oxidation1–6 is a simple and effective method for the conversion
and/or destruction of many organic and inorganic compounds with a mea-
surable rate up to negligible concentration levels. On these grounds, it is very
suitable for solving various problems of environmental interest in water
purification.
The process is not complex: irradiation of the semiconductor surface with
light of band gap (or higher) energy generates very reactive species able to
break the molecular bonds of chemicals until only carbon dioxide and water are
left. Titanium dioxide, a very safe, common and inexpensive material, has
proven to be the most effective photocatalyst for breaking down a wide range of
chemicals, without producing harmful by-products. Owing to these favorable
features, this method is starting to be used to solve real problems raised by the
presence of pollutants in water. In the following some field applications are
described.
7.1.1 Pesticide Degradation in a Solar Photoreactor

Solar photocatalysis is today one of the most successful applications of this
advanced oxidation process. In Europe the development and scale-up of solar
photocatalytic applications is successfully carried out at the Plataforma Solar
de Almerı́a (PSA, Spain), which, due to such strong activity carried out, has
become a benchmark worldwide. One of the relevant projects has been the
SOLARDETOX (EC-DGXII BRITEEURAM-III program) on solar photo-
catalytic detoxification of water.7 The project objective was to develop a simple,
efficient and commercially competitive water-treatment technology, based on
compound parabolic solar collectors (CPCs) and TiO2 photocatalysis to make
possible easy design and installation. The result of that project was the design,

199
200 Chapter 7
Figure 7.1 View of the solar CPC collector field (Arganda del Rey, Madrid, Spain).
set-up and operation of the first European industrial solar detoxification

treatment plant at Arganda del Rey (Madrid, Spain). The irradiated surface of
the CPCs is of 100 m2; Figure 7.1 shows a view of the demonstration plant.
The SOLARDETOX research has also allowed the construction and
operation of one of the first commercial plants, implemented by the Spanish
company Albaida. With the aim of recycling the huge number of pesticide
bottles needed for greenhouse agriculture activity in Almerı́a province (Spain),
the Albaida plant treats the washing water of the plastic bottles.
Figure 7.2 shows the conceptual design of the solar photocatalytic treatment
plant. The water containing pesticides coming from the bottle-washing process
is decontaminated in a batch solar photoreactor until 80% mineralization of
TOC is achieved. Solar decontamination is carried out by coupling photo-
catalysis and photo-Fenton methods.8 The treated water is then transferred to
the post-process treatment (i.e., sedimentation and recuperation of photo-
catalyst, iron precipitation) and then reused for the washing process or dis-
charged for irrigation. Figure 7.3 shows the system used for recuperation of
TiO2 and Fe21, while Figure 7.4 shows the solar collector field of the Albaida
plant.
7.1.2 Cyanide Degradation in a Pilot Plant Photoreactor

To degrade free cyanide ions contained in power plant wastewater, a con-
tinuously stirred tank photoreactor at pilot plant level has been designed,
constructed and tested. The working power plant, located at Puertollano
(Spain), utilizes an integrated gasification combined cycle based on a coal
gasification process.9 The photoreactor for cyanide degradation was arranged
in parallel with the chemical treatment performed on the gross contaminated
Devices for Water and Air Purification 201
Chemical
Photocatalyst Oxidant
Mixer
Oxygen
(Air)
Tank
Solar UV
light
Filter Pump
DETOXIFICATION Contaminated
CYCLE Water
Photoreactor CPC
solar collector field
TOC TOC
<100 ppm >100 ppm
Discharge
(irrigation WASHING
Water) CYCLE
Yes
Reutilization?
No
GAC filter
Industrial bottles
Washing process
Figure 7.2 Conceptual design of the Albaida solar photocatalytic process.
effluent of the industrial plant. Figure 7.5 gives a block diagram of the
decontamination process; blocks other than the photoreactor represent existing
units of the water treatment system of the plant. The photoreactor was designed
to treat a flow rate of 1 m3 h1 of the liquid effluent feeding the ozonization
reactor and to perform a 98% conversion of cyanides.
202 Chapter 7
Figure 7.3 TiO2/Fe21 recuperation system. (Reproduced with permission from

ref. 8.)
The reactor configuration chosen to perform cyanide oxidation at the pilot

plant scale was that of a continuous slurry stirred tank reactor with immersed
lamps. The choice of this photoreactor is based on the following considerations:
(i) by increasing the catalyst concentration, a maximum of activity, i.e., of local
volumetric reaction rate, can be reached; (ii) mass transport resistance between
the bulk of the liquid phase and the irradiated surface of the catalyst can be
minimized depending on the agitation degree of the system; and (iii) the irra-
diation efficiency, i.e., the ratio between the total photon flow emitted by the
lamp and that absorbed by the whole suspension, can approximate unity as the
catalyst concentration of the suspension can be chosen in order that no
radiation is transmitted by the suspension.
The main operative drawback of a continuous slurry reactor is that the exit
flow consists of the internal reacting suspension so that wash out of the catalyst
eventually occurs. It is therefore necessary to employ solid–liquid separation
equipment coupled with the reactor to recover the catalyst and a solid conveyor
for recycling the catalyst to the photoreactor. To avoid the need of the
Figure 7.4 Industrial solar photocatalytic water treatment plant for pesticide-bottle
recycling (La Mojonera, Almerı́a, Spain) (150 m2 of total collector
surface).
separation–transportation unit, the photoreactor has been designed with an

inside settling zone so that the exit flow does not contain solid particles. This
choice allows one to simplify the photoprocess operation but means that the
catalyst particles must possess certain features; in particular the particles should
have a high settling velocity.
Literature information on the kinetics of cyanide photodegradation and on
the quantum yield of the photoreaction10–12 was used to calculate the reacting
volume of the photoreactor and the irradiation power. The following values
were used for the photoreactor set-up: reactor ‘‘design’’ volume: 0.84 m3;
security factor of 2.5; with previous values the reacting volume of the photo-
reactor is 2 m3. Figure 7.6 shows the scheme of the photoreactor. The reacting
volume is cylindrical (1500 mm in diameter and 1700 mm high). In the scheme
of the photoreactor an outer annular zone is allowed to separate the catalyst
particles from the liquid solution leaving the reactor. In this way the outer
204 Chapter 7
Plant waste water
Stripper
Primary Ozone
Effluent settler oxidation
Sewer
Coagulant
flocculation
Photoreactor
Figure 7.5 Block diagram of the decontamination process; blocks other than that for
the photoreactor represent existing units of the water treatment system of
the IGCC plant.
electric motor
lamp
support inlet 1500
outlet
Pyrex tubes
2000
support
1700
2500
Pyrex 500
tube
propeller
150
140
Sedimentation zones
(A) (B)
Figure 7.6 (a) Scheme of the pilot plant photoreactor; (b) photoreactor top view,
showing the distribution of Pyrex tubes containing the lamps. The figures
indicate millimetres.
diameter of the photoreactor is 1800 mm. A rotating pump feeds the liquid flow
to the photoreactor while the exit stream leaves the photoreactor by gravity.
The irradiating system consists of 16 Pyrex cylindrical tubes (ca. 2 m long), each
of which contains eight fluorescent actinic lamps (40 W, 60 cm high). The
reacting mixture is mixed by a turbine impeller (500 mm diameter) with inclined
blades in order to obtain a high axial flow. The impeller is positioned at about
1/6 of the liquid height from the bottom in order to better suspend the catalyst
particles. Figures 7.7 and 7.8 are photographs of the photoreactor and of some
details.
Figure 7.7 Picture of (a) the photoreactor; (b) view of the external vessel and jacket of
the photoreactor; (c) the photoreactor cover; (d) view of the outlet of the
photoreactor.
206 Chapter 7
Figure 7.8 Picture of (a) the control system panel used to check the correct working
order of the lamps; (b) view of the opening that allows the reacting volume
to be in contact with the atmosphere; (c) stainless steel support of the
Pyrex tubes; (d) Pyrex tube with the support containing eight lamps.
The catalyst was TiO2 supported on Al2O3 particles. The supported catalyst
had a TiO2 content of 53 wt%; it exhibited a high reactivity while maintaining
long-term mechanical stability. The reactivity runs carried out on the power
plant wastewater showed a cyanide conversion higher than 98%.
The main merit of this pilot plant investigation has been the demonstration
of the feasibility of a process for cyanide degradation by mean of heterogeneous
photocatalytic method at the industrial level. The good performance of the
pilot plant photoreactor allows one to obtain a liquid effluent with a con-
centration of free cyanide far below the 0.5 ppm that is the maximum allowable
value according to EC environment protection law.
7.1.3 Photo-CREC-Water Reactors
Researchers at the Chemical Reactor Engineering Centre (CREC)13 of the
University of Western Ontario (Canada) have designed and constructed
photocatalytic reactors (either for gas–solid or liquid–solid regime) under
the optimality criteria of improved efficiency and improved irradiation of the
photocatalyst.
Three photocatalytic reactors for water treatment have been produced:
1. Photo-CREC-Water I with immobilized TiO2;

2. Photo-CREC-Water II, with suspended TiO2 and artificial irradiation;
3. Photo-CREC-Water III, with suspended TiO2 and simulated solar
irradiation.
The original Photo-CREC-Water I reactor14,15 has been modified with respect

to the original design by Serrano and de Lasa.16 Figure 7.9 is a schematic
representation of the photocatalytic reactor.
The Photo-CREC-Water I reactor is characterized by an annular channel
with 16 baskets positioned at 451 angles. Stainless steel spacers placed between
the baskets secure the baskets in position.
The near-UV lamp is located in the central channel, providing monochro-
matic light at 365 nm. Water is circulated in a downward flow; water at the
photoreactor outlet is discharged into an air bubbler that guarantees saturation
with oxygen.
Figure 7.9 Schematic representation of the Photo-CREC-Water I reactor: (a) com-

pressed air, (b) air gas regulator, (c) oxygenator with air pipe distributor,
(d) water pump, (e) valve, (f ) concentric Photo-CREC unit with lamp
placed in the center and 16 conical baskets spaced throughout the unit, (g)
three-way valve, (h) lamp, (i) basket, ( j) Pyrex glass tube, (k) external
Plexiglas tube and (l) annular channel. (Reproduced with permission from
ref. 16.)
208 Chapter 7
The core of the Photo-CREC Water I is the photocatalytic basket containing
the TiO2-mesh. Before TiO2 impregnation, the fiber-glass mesh is treated with a
nitric acid solution and afterwards it is calcined at 550 1C for a few hours.
The mesh is then mounted on the inner face of each of the conical baskets and
‘‘in situ’’ impregnated by circulating a TiO2 slurry through it. Strong attach-
ment of TiO2 particle on the fiberglass mesh was established16 when translucent
water was obtained after the first washing of meshes and in all subsequent
experiments, confirming that the Photo-CREC-Water I reactors do not require
particle recovery.
The Photo-CREC Water-II reactor consists of two concentric Pyrex tubes
with a TiO2 suspension flowing in the concentric channel; a UV lamp irradiates
the catalyst from the inner tube. Figure 7.10 illustrates the components of this
reactor.
The inner tube may be changed so varying the dimension of the annular
cross-section and the fluid dynamics of the circulating suspension. A stirred
tank is connected in series with the photoreactor. The tank allows sampling,
pollutant and catalyst addition, pH and temperature monitoring and oxygen
saturation of suspension. The unit is equipped with windows along the outer
tube wall in order to perform radiometric and spectro-radiometric measure-
ments. A four-point flow distributor injector at the reactor entrance guarantees
uniform injection and intense mixing.
With respect to the Photo-CREC Water II, the Photo-CREC Water-III
reactor (Figure 7.11) shows the following main features: (i) external illumina-
tion simulating solar irradiation; (ii) larger irradiation area; (iii) presence of
Figure 7.10 Schematic representation of the Photo-CREC Water-II Reactor: (1)

lamp, (2) and (3) replaceable inner tube, (4) fused-silica windows, (5) UV-
opaque outer tube, (6) stirred tank, (7) pump and (8) air injector.
Figure 7.11 Schematic representation of the Photo-CREC Water-Ill reactor.

internal sensor to measure the radiation field; and (iv) internal irradiation to
make uniform the radiation field in radial directions. The reactor is irradiated
externally by UV lamps. The external illumination permits the simulation of
solar irradiation whereas the combination of internal and external illumination
allows the increase of irradiation efficiency.
The bench-scale Photo-CREC reactors maximize the catalyst–liquid contact
and the efficiency of light–TiO2 interaction;17 on this basis they facilitate the
study of important reaction engineering parameters such as the adsorption and
the reaction rates of model compounds, the photodegradation mechanisms and
the photocatalyst performance.
Photo-CREC Water reactors have been successfully used in the photo-
conversion of many organic and inorganic pollutants, as well as the inactivation
of microorganisms contained in water. A semi-commercialized version of the
Photo-CREC unit (Figure 7.12) has a water treatment capacity of 300 l,
addressing the basic daily needs of a community of 500 people (around 1200 l
day1). Research is underway to increase the Photo-CREC reactor’s capacity,
with the goal of supplying drinking water to communities of 3000 people.
7.1.4 UBE Photocatalytic Fiber Reactor

UBE Group,18 using technologies created in the development of an ultra-high
temperature resistant ceramic, has successfully developed a photocatalytic fiber
with a large surface area and good fiber strength. The fiber contains titania
photocatalyst so that it is able to oxidize and decompose organic substances.19
210 Chapter 7
Figure 7.12 Semi-commercialized version of the photo-CREC water reactor.

The photocatalytic fiber is arranged in a very simple purifier with a module

composed of the cone-shaped felt material (made of the photocatalytic fiber)
and a UV lamp. Figure 7.13 shows the set-up of the total recirculation photo-
reacting system. The contaminated water, contained in a reservoir, is con-
tinuously fed to the photoreactor, where the contaminants are destroyed. The
photocatalytic fiber can purify not only the many types of wastewater but can
also destroy bacteria present in wastewaters. Many bacteria (common bacter-
ium, Legionella pneumophila and coliform)20 that exist in bathwater before
purification are rapidly decomposed into CO2 and H2O. Figure 7.14 shows the
behavior of cell concentration versus irradiation time for a deactivation run
carried out with the UBE photoreactor on wastewater contaminated by
Legionella and aerobic bacteria. Figure 7.15 shows a UBE photocatalytic
device with a fiber module.
7.2 Devices for Air Purification

People inhale 15–18 kg of air every day. If living in contaminated areas, a
person also inhales on average a 15–100 mg daily dose of poisonous substances
such as carbonic oxide, formaldehyde, benzopyrene and many other
Figure 7.13 Set-up of the UBE photoreacting system. (Reproduced with permission
from ref. 18.)
detrimental compounds that in big cities are in large excess over permissible
rates. It is, therefore, of great concern to purify, as much as possible, the air of
enclosed sites.
Heterogeneous photocatalysis is one of the most efficient and cost-effective
air purification technologies, and scientists predict that it would be the main
method of air purification in the near future. Photocatalytic methods for indoor
air purification have considerable advantages over other methods. Unlike air
purification by adsorption, photocatalytic oxidation leads to complete neu-
tralization of air pollutants, forming CO2 and H2O as final products, and no
regular regeneration of the photocatalyst is usually required. Almost any
212 Chapter 7
Figure 7.14 Cell concentrations versus irradiation time for a run with Legionella
without catalyst (B) and for photocatalytic runs with Legionella (J) and
with aerobic bacteria (&); K and ’ indicate the initial concentration of
Legionella and aerobic bacteria, respectively. (Reproduced with permis-
sion from ref. 20.)
Figure 7.15 UBE photocatalytic device: (a) fiber module; (b) fiber cartridge.
organic substance, even at low concentration, can be oxidized under ambient
conditions using air oxygen. Owing to these favorable features, the photo-
catalytic method has attracted the attention of industry devoted to producing
apparatuses for air conditioning; here the objective is purify the indoor air of
homes, hospitals, farms, etc.
In some purifying apparatuses the photocatalytic method is coupled
with the generation of negative or positive air ions.21 These charged particles,
such as O2, O, OH, (H2O)x, N21, O1, O2þ , NO1, CH4þ , NH4þ , and so on,
are widely distributed in natural air and are generated by radioactive elements
in the soil, cosmic rays, radioactive aerosols, UV radiations, and many other
phenomena. Temperature and humidity strongly affect the mean lifetimes
of air ions; in most cases lifetimes vary from several seconds to thousands of
seconds.22 This feature is beneficial as a high concentration of negative
air ions is conducive to microbial sterilization. Moreover, it is known that air
ions may affect the moods of people; a high proportion of negative ions
in the air makes people feel lively, uplifted and enthusiastic, while too many
positive ions will leave people feeling depressed, lethargic and full of aches,
pains and complaints. Negative air ions are considered to be a living resource
for human beings, leading to the widespread use of air ionizers. The following
presents some commercial apparatuses, both photocatalytic and photo-
catalytic/ionizer.
7.2.1 Photo-CREC-Air Reactor

For air treatment, researchers at the Chemical Reactor Engineering Centre
(CREC)13 of the University of Western Ontario (Canada) have designed and
constructed the Photo-CREC-Air unit with a Venturi design and TiO2
anchored on an irradiated mesh.23–26 Figure 7.16 shows a schematic diagram of
the unit set-up.
The main body of the closed-loop system is made of zinc-plated pipes con-
nected with aluminized-steel 901 elbows and a stainless steel Venturi section.
External lamps irradiate the reaction section. Radiation penetrates through
windows placed in the divergent section of the Venturi. Pen-Ray lamps are
symmetrically placed around the reaction section and housed in reflectors for
uniform irradiation distribution. The reaction section is formed by a basket
supporting a fiber-glass mesh impregnated with TiO2.
The Photo-CREC-Air unit operates in batch mode with a given amount of
model pollutant injected in a set volume of air. Model pollutants are vaporized
almost instantaneously and mixed intimately with the air stream. A favorable
feature of this reactor is that it provides the highest gas velocity in the near-
window region, ensuring a high degree of window sweeping and preventing
TiO2 particle deposition on the windows.
The bench-scale Photo-CREC-Air unit shows the same useful features
as the Photo-CREC-Water reactors (high mixing and catalyst–gas contact,
efficient light–TiO2 interaction) and it is highly suited for investigation
purposes.
214 Chapter 7
Figure 7.16 Schematic diagram of the Photo-CREC-Air unit set-up. (Reproduced

7.2.2 AirSteril Purifier

The AirSteril air purifier27 (Figure 7.17) uses ultraviolet germicidal light (UVC,
253.7 nm) together with a photocatalyst (nanostructured TiO2 supported on
plates) to kill airborne pathogens (viruses, bacteria, fungi, etc.) and at the same
time to decompose odors as well as harmful gases. Indoor air pollutants are
converted into harmless substances such as CO2 and water vapor by the
multistage nano-titanium dioxide coated base plates. Negative ions generated
by the strong UVC irradiation of air can also remove airborne positively
charged dust particles and pollen through attraction rendering them too heavy
to remain airborne.
Table 7.1 describes some characteristics of AirSteril device.
7.2.3 Airlife Purifier

Figure 7.18 shows the working scheme and a photograph of the Airlife air
cleaner.28 These photocatalytic air purifiers are equipped with a special porous
carrier with a TiO2 photocatalyst, which adsorbs the light quanta and through
which the air flows. The main function of the TiO2 photocatalyst is to adsorb
Figure 7.17 Details of the AirSteril air purifier. (Reproduced with permission from
ref. 27.)
Table 7.1 Some features of the AirSteril device.

Feature Specification
UVC lamp tube 13 W composite tube
UVC intensity inside chamber 10 mW cm2
UVC lamp tube life 8000 h
Number of photocatalyst base plates 3
Dimensions (length width height) 350 130 1000 mm
Air flow rate 20 m3 h1
Power consumption 25 W
Covering area 25–50 m2 (hospital/clinic 10–25 m2)
Installation Wall mount/table top
Quantity of ozone produced 8–80 mg h1
organic and inorganic contaminants that are then decomposed into CO2 and
H2O under the influence of the UV lamp, which irradiates with mild ultraviolet
light at a wavelength less than 300 nm (A-range). The reaction runs at room
temperature.
Airlife Purifiers have been tested in degradation experiments of organic and
inorganic substances at the Novosibirsk Institute of Catalysis. In addition,
experiments on the pathogenic viruses and bacteria elimination have been
carried out at the Novosibirsk Scientific Research Institute of Tuberculosis.
7.2.4 Daikin Purifier

Daikin air purifiers, designed for use in residences and small commercial
premises, utilize a two-stage electrostatic plasma ionizer combined with a
216 Chapter 7
Figure 7.18 Working scheme and photograph of the Airlife Purifier device. (Repro-
titanium dioxide photocatalytic filter and UV light.29 The indoor climate is

enhanced still further by means of negative ion generation, allowing purified air
to be refreshed and circulated throughout the conditioned space, adding a
natural and spring-like quality to the atmosphere.
Daikin air purifiers consist of (i) a prefilter in which large dust particles
and pet hairs are captured and the bacteria and mould spores attached
to them are removed by a polyphenolic antioxidant (catechin); (ii) a bio-
antibody filter in which airborne viruses are quickly adsorbed by the bio-
antibodies and then rapidly removed; (iii) a flash streamer consisting of a
plasma ionizer in which fine dust and pollen are positively charged; (iv) an
electrostatic dust collection filter in which the positively charged sub-
stances are adsorbed by a negatively charged filter; (v) a titanium apatite
photocatalytic filter in which organic substances, mould spores and viruses are
adsorbed and removed; and (vi) a streamer deodorizing catalyst in which odors
are removed.
Figure 7.19 shows photographs of Daikin air cleaners and Figure 7.20 gives
the scheme of their working principle. Figure 7.21 illustrates how the flash
streamer unit works.
Figure 7.19 Daikin air purifier models. (Reproduced with permission from ref. 29.)
7.2.5 Genesis Air Purifier

Genesis Air30 incorporates the Genesis Air Photocatalyst Gapt technology to
oxidize airborne biologics and volatile organic compounds.
To achieve air quality a synergistic approach is realized in a three-step
process: (i) capture by filtration of particles such as pollen, mold, mildew, house
dust, bacteria, etc., (ii) cleaning by ultraviolet lamps and (iii) photocatalytic
conversion that produces hydroxyl radicals (oxidant primary species) able
to oxidize biologics in the air stream and volatile organic compounds.
Figures 7.22–25 show some Genesis purifiers and their applications.
7.2.6 Airwises Purifiers

Airwise31 is based on a technology that does not need mechanical filtration
methods. Airwises technology oxidizes odors, fungi, mold and parasites, and
toxic chemical gases. At the same time, it settles dust and other large particles
out of the air and destroys microorganisms like bacteria and viruses.
Figure 7.26 shows the scheme and a photograph of this purifier. Airwises
creates inductive warmth, drawing humidity into the purifier. When humidified
air enters the target area, a photocatalytic reaction occurs and superoxide ions
and hydroxyl radicals are created. As an added benefit, positively charged
indoor pollutants are treated by active negative ions generated at an accelerated
rate, thereby enhancing the speed at which dust and other airborne particles
drop out of the breathing space. Airwises technology works ‘‘outside of the
box’’ so it is not necessary for polluted air to actually enter the purifier. This
process significantly reduces allergens such as pollen and it destroys viruses,
218
Chapter 7
Figure 7.20 Scheme of the working principle of Daikin air purifiers. (Reproduced with permission from ref. 29.)
Devices for Water and Air Purification
Figure 7.21 Scheme of the flash streamer unit of Daikin air purifiers. (Reproduced with permission from ref. 29.)
219
220 Chapter 7
Figure 7.22 Stand-alone system designed to fit in a grid ceiling. (Photograph courtesy

of ref. 30.)
bacteria, mold and mildew. Airwises needs no fan and it has no grid or filter,
so it requires no cleaning or filter replacement.
7.2.7 ‘‘Luch’’ Series Cleaners

Air cleaners of the ‘‘Luch’’ series32 are intended for the purification and dis-
infecting of air in living quarters and administrative rooms, schools, medical
establishments, libraries, etc. Table 7.2 shows the characteristics of the devices.
Figures 7.27 and 7.28 show the working scheme of Luch-22 and Luch-60 Air
cleaners, respectively (photographs given in Figure 7.29).
The unit operation is based on the photocatalytic oxidation of organic
admixtures on the photocatalyst surface under mild UV-radiation.33 In this
way it can neutralize various toxic compounds and microorganisms that are not
Figure 7.23 Standard photocatalytic purifiers that may be installed in supply or

return ducts. (Photograph courtesy of ref. 30.)
amenable to traditional (adsorptive, electrostatic, catalytic) methods. The

range of pollutant concentrations for effective destruction is 1 to 10 admissible
concentration limits.
7.2.8 Aero Super Element Cleaners

The photocatalytic air cleaner Aero Super Element34 is an ecologically safe
device for clearing and decontaminating air. Figure 7.30 shows the device.
The Aero Super cleaner is particularly recommended for use in anti-
tubercular and other medical institutions, including premises with a normalized
level content (surgeries, dressing examinations, intensive care units, labor
222 Chapter 7
Figure 7.24 Wall mounted or portable reduced size gaming special unit. (Photograph
courtesy of ref. 30.)
wards, laboratories, drugstores, isolation wards), and also in all other premises
that require a high degree of decontamination and cleaning of air.
Aero Super devices are designed for continuous working and they guarantee
a high efficiency of decontamination and cleaning of air. The decontaminating
agent provides a high degree of air decontamination, two and more times larger
than existing methods of air decontamination (bactericidal lamps). The ultra-
violet radiation band (320–400 nm) used and low noise level (up to 32 dB)
permit comfortable use of device for 24-hour action.
7.2.9 Zand-Air Cleaners

The ZAND-AIRt 200 system35 incorporates leading-edge photocatalysis and
high-efficiency particle filtration, and converts volatile organic compounds and
chemically active compounds into water and carbon dioxide, while capturing
sub-microscopic-particles.
This system is designed for in-line, ducted multiphase filtration systems and
it may be incorporated in new or existing construction and renovations to
provide protection for people and laboratory environments against indoor air
pollutants. The uniqueness of this product lies in its ability to clean and
eliminate all pollutants within the capacity of existing blowers and filtration
equipment. Figure 7.31 shows the set-up of the apparatus.
The first step of the purification process is the adsorption of toxic chemicals
and gases: the activated carbon filter in the front position adsorbs organic
Figure 7.25 Genesis unit designed to be ceiling mounted or portable on casters.

(Photograph courtesy of ref. 30.)
hydrocarbons, volatile organic compounds, chemically active compounds and

other harmful agents. Microparticles are then removed by a high efficiency
particulate air (HEPA) filter, capable of removing at least 99.97% of airborne
particles (pollen, mold, bacteria, etc.) 0.3 mm in diameter. The next step is the
destruction of toxic chemicals and odors by photocatalytic oxidation: the
oxidation converts malign toxic compounds (even carbon monoxide and
nitrous oxide) into benign constituents such as H2O and CO2. The catalyst is
such that it does not wear out or lose its effectiveness as a result of its actions.
The last step consists of purification by ultraviolet light: the ultraviolet light
attacks the molecular structure of viruses and bacteria, which are too small to
be filtered out by the HEPA filter, thus rendering them harmless.
Figure 7.32 shows, viewed from below, three ZAND-AIRt 200 units
installed in frames as a battery below the roof, above a drop ceiling, mounted
224 Chapter 7
Figure 7.26 Airwises air purifier. (Photograph courtesy of ref. 31.)
Table 7.2 Specifications of air cleaners of the Luch series.

Parameter LUCH-22 LUCH-60 LUCH-400
Power consumption (W) 25 100 1100
Air flow (m3 h1) 23 40/85/130 600–1500
Noise level (dB) Up to 34 40–55 30–70
Photocatalyst lifetime (years) 5 10 10
Weight (kg) 1 7 62
Dimensions (mm) Diameter 260; 345 175; 1625 555;
height 74 height 500 height 855
into the air conditioning enclosure. The units may be unplugged for removal
and servicing outside of their frame structures.
Figure 7.33 shows a system suitable for clean air inside laboratories.
7.2.10 Comefresh Electronic Industry Cleaner

The air cleaner of Comefresh Electronic Industry36 uses the technology of a
four-stage filtration process: (i) HEPA filter; (ii) an ultra-low particulate air
(ULPA) filter theoretically able to remove from the air at least 99.999% of dust,
pollen, mold, bacteria and any airborne particles 120 nm or larger in size; (iii)
UV light, photocatalyst filter; and (iv) activated carbon filter. In this way the
cleaner ensures the removal of particles, harmful vapors, odors and volatile
organic compounds; moreover, it traps pollen and kills bacteria and viruses.
Figure 7.34 shows a photograph of the Comefresh air cleaner.
Figure 7.27 Luch-22 photocatalytic air cleaner produced at the Luch NPO (Novo-
sibirsk, Russia): 1, UV lamp; 2, contaminated air; 3, ventilator; 4, pur-
ified air; 5, case; and 6, filter with photocatalyst. (Reproduced with
Fan
Air outlet
Filter
UV lamps
Filter
Electrostatic Filter
Photocatalytic
fibers
Air inlet
Figure 7.28 Working scheme of Luch-60 Air cleaner. (Reproduced with permission
from ref. 32.)
226 Chapter 7
Figure 7.29 Photograph of Luch-22 and Luch-60 Air cleaners. (Photograph courtesy
of ref. 32.)
Figure 7.30 Photograph of an Aero Super Element air cleaner. (Photograph courtesy
of ref. 34.)
7.2.11 Airpura Purifiers

Airpura air purifiers37 give particular attention to air flow. While in other
systems air moves around different chambers and changes direction, Airpura
simplifies air flow for quieter more efficient performance, so it reduces noise. All
of the air is filtered and no particles or gases escape the filters so that the
Figure 7.31 Set-up of ZAND-AIRTM 200. (Photograph courtesy of ref. 35.)
Figure 7.32 Typical ZAND-AIRTM 200 installation. (Photograph courtesy of

ref. 35.)
228 Chapter 7
Figure 7.33 A zIVF-AIRe 100C CLEAN AIRt unit, a system that provides air fil-
tration and purification for IVF laboratories. (Photograph courtesy of
ref. 35.)
claimed 99.97% HEPA efficiency may be achieved. Figure 7.35 gives a picture
and working scheme of an Airpura 600 Series purifier.
The core of the apparatus is the TitanClean reflector, the surface area of
which is coated with an optimized amount of TiO2. The angled reflector design
maximizes the range of photocatalytic oxidization within the filter chamber.
The location of the TitanClean reflector and the UV light in the centre of the
filter chamber allows them to work in concert with the HEPA filter. Particulate
pollution is stopped by the HEPA filter before reaching the reflector. This keeps
the coated surface cleaner and more effective.
The UV germicidal lamp does not generate ozone and it maintains 98% of its
antigen and pathogen destruction effect due to the interior position of the
reflector. Contact time of airborne chemicals is increased as they slow down on
passing through the HEPA. Diffusion of the germicidal dosage from the UV
lamp is enhanced in the confined chamber.
Figure 7.34 Photograph of a Comefresh air cleaner. (Photograph courtesy of ref. 36.)
Figure 7.35 Picture and working scheme of an Airpura 600 Series purifier. (Photo-
graph courtesy of ref. 37.)
7.2.12 Air Oasist Purifier

In Air Oasist purifier38 apparatuses the photocatalytic method is coupled with
the generation of negative air ions.21
230 Chapter 7
Figure 7.36 Picture and working scheme of an Air Oasist purifier. (Photograph
courtesy of ref. 38.)
Figure 7.37 Picture of an Air Sterilizer ‘‘Medicare.’’ (Photograph courtesy of ref. 39.)
The Air Oasist purifiers utilize a high-performance TiO2 catalyst placed
on an advanced hydrated photocatalytic oxidation (AHPCOTM) cell. The
AHPCO cell consists of a high-intensity broad spectrum UV tube in a
hydrated catalytic matrix cell that generates hydroperoxides, superoxide ions,
hydroxyl ions, negative ions and ozonide ions that are released to air
circulating through the cell, providing protection against airborne fungi, bac-
teria, viruses, odors and volatile organic compounds. Low-level ozone is pro-
duced in the cell, most of which is converted into airborne hydroperoxides and
hydroxyl ions via the metallic catalyst. The photogenerated ions treat indoor
air by suppressing bacteria and fungi growth, volatile organic compounds and
reducing odors. Figure 7.36 shows a picture and working scheme of an Air
Oasist purifier.
7.2.13 Air Sterilizer ‘‘Medicare’’

This photocatalytic purifier39 uses a honeycomb photocatalyst for sterilizing
air. The fiber structure of the photocatalyst maximizes the surface in contact
with air, thus giving a high efficiency to the system. In this way it can remove
ordinary bacteria, dust, toxic substances and offensive odors and prevent
respiratory diseases. Figure 7.37 shows an Air Sterilizer ‘‘Medicare.’’
7.2.14 Photocatalytic Cold Fluorescent Lamp

A titanium dioxide layer coats the bulb of these lamps,40,41 which have a
standard base socket (Figure 7.38). The fluorescent light bulb uses fluore-
scent light and TiO2 to transform tiny air particles and toxic gases into
safer substances. In this way fresh, clean air is created through a product
Figure 7.38 A photocatalytic cold fluorescent lamp. (Photograph courtesy of ref. 40.)
232 Chapter 7
that is maintenance-free as there are no air filters to replace or collecting grids
to clean.
References
1. M. Schiavello (ed.), Photocatalysis and Environment. Trends and Applica-
tions, Kluwer Academic Publishers, Dordrecht, 1988.
2. D. F. Ollis and H. El-Ekabi (eds), Photocatalytic Purification and
Treatment of Water and Air, Elsevier Science Publishers, New York,
1993.
3. M. Schiavello (ed.), Heterogeneous Photocatalysis, Wiley Series in
Photoscience and Photoengineering John Wiley & Sons, vol. 3, Chichester,
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4. M. Schiavello (ed.), Photoelectrochemistry, Photocatalysis, and Photo-
reactors, Fundamentals and Developments, Reidel, Dordrecht, 1985.
5. E. Pelizzetti and N. Serpone (eds), Homogeneous and Heterogeneous Photo-
catalysis, Reidel, Dordrecht, 1986.
6. N. Serpone and E. Pelizzetti (eds), Photocatalysis, Fundamentals and
Applications, John Wiley & Sons, Chichester, 1989.
7. S. Malato, J. Blanco, A. Vidal, P. Fernández, J. Cáceres, P. Trincado, J. C.
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8. J. Blanco, S. Malato, P. Fernández, D. Alarcón, W. Gernjak and M. I.
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1274-4, Eindhoven, 2008. Available online at http://www.eurotherm2008.
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9. V. Augugliaro, J. C. Conesa, E. Garcı́a López, V. Loddo, M. J. López
Muñoz, G. Marcı́, L. Palmisano, M. Schiavello and J. Soria, Pilot pho-
toreactor for cyanides degradation, Chim. Ind., 2001, 83, 34.
10. V. Augugliaro, V. Loddo, G. Marcı̀, L. Palmisano and M. J. López-
Muñoz, Photocatalytic oxidation of cyanides in aqueous titanium dioxide
suspensions, J. Catal., 1997, 166, 272–283.
11. V. Augugliaro, J. Blanco Gálvez, J. Cáceres Vázquez, E. Garcı́a López, V.
Loddo, M. J. López Muñoz, S. Malato Rodrı́guez, G. Marcı̀, L. Palmi-
sano, M. Schiavello and J. Soria Ruiz, Photocatalytic oxidation of cyanide
in aqueous TiO2 suspensions irradiated by sunlight in mild and strong
oxidant conditions, Catal. Today, 1999, 54, 245–253.
12. V. Augugliaro, E. Garcı́a López, V. Loddo, G. Marcı̀ and L. Palmisano,
Degradation kinetics of iron(III) cyanocomplexes in irradiated systems,
Adv. Environ. Res., 1999, 3, 179–188.
neering, Springer, 2005.
14. J. Valladares, A new photocatalytic reactor for the photodegradation of
organic pollutants in water. Ph.D. Dissertation, University of Western
Ontario, London, Canada, 1995.
15. H. I. de Lasa and J. Valladares, Photocatalytic reactor, US Pat. No.
5683589, 1997.
16. B. Serrano and H. I. de Lasa, Photocatalytic degradation of water organic
pollutants. Kinetic modeling and energy efficiency, Ind. Eng. Chem. Res.,
1997, 36, 4705–4711.
17. B. Serrano, A. Ortı́z, J. Moreira and H. I. de Lasa, Energy efficiency in
photocatalytic reactors for the full span of reaction times, Ind. Eng. Chem.
Res., 2009, 48, 9864–9876.
18. http://www.ube-ind.co.jp/english/rd/business.htm
19. T. Ishikawa, Photocatalytic fiber with gradient surface structure produced
from a polycarbosilane and its applications, Int. J. Appl. Ceram. Technol.,
2004, 1, 49–55.
20. J. M. Coronado, J. Soria, J. C. Conesa, R. Bellod, C. Adán, H. Yamaoka,
V. Loddo and V. Augugliaro, Photocatalytic inactivation of Legionella
pneumophila and an aerobic bacteria consortium in water over TiO2/SiO2
fibres in a continuous reactor, Top. Catal., 2005, 35, 279–286.
21. J. Zhang and Z. Yu, Experimental and simulative analysis of relationship
between ultraviolet irradiations and concentration of negative air ions in
small chambers, Aerosol Sci., 2006, 37, 1347–1355.
22. L. Aare and P. Tiia, Evolution of negative small air ions at two different
temperatures, J. Atm. Solar-Terrestrial Phys., 2002, 64, 763–774.
23. H. Ibrahim, Photocatalytic reactor for the degradation of airborne pollu-
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pollutants. Effect of catalyst type and catalyst loading in a novel photo-
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27. http://www.airpurifier.com.hk/product-en.htm
28. http://www.vozdyx.ru/eng/foto.shtml
29. http://www.daikin-air-purifiers.co.uk
30. http://www.genesisair.com/products.html
31. http://www.simply-natural.biz/airwise.php
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234 Chapter 7
36. http://comefresh.manufacturer.globalsources.com/si/6008821537308/
Homepage.htm
37. http://www.nontoxic.com/airpura/airpura.html
38. http://www.peakpureair.com/airoasis.htm
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Medicare_.html
40. http://www.purion.ie/component/virtuemart/category/6/bulbs.html
41. http://www.germfreebulb.com/howitworks.html
CHAPTER 8
Standardization
8.1 Introduction
Standardization is defined as ‘‘the activity consisting of the processes of for-
mulating and implementing documents (the standards) that provide rules or
characteristics for activities or their results, aimed at the achievement of the
optimum degree of order in a given context.’’ Science, technology and experi-
ence contribute to issue standards, whose main benefits are improvement of the
suitability of products, processes and services, prevention of technical barriers
to trade and facilitation of technological cooperation.
Three bodies are responsible for the planning, development and adoption of
International Standards: the International Electrotechnical Committee (IEC) is
responsible for electrotechnical sector, the International Telecommunication
Union (ITU) for most telecommunications technologies and the International
Organization for Standardization (ISO) for all the other sectors, including
heterogeneous photocatalysis.
ISO1 is a legal association, the members of which are the National Standards
Bodies representing social and economic interests at international level. The
principal deliverable of the ISO is the International Standard, the main features
of which are openness and transparency, consensus and technical coherence.
These principles are followed by the ISO Technical Committee (ISO/TC),
which is the technical body responsible for the planning and execution of the
work.
In the field of heterogeneous photocatalysis, even though the photocatalysis
industry has grown very much in the last 10 years, the lack of standard eva-
luation methods for photocatalytic products hinders consumer understanding
of the performance of photocatalytic products and the ability to compare
correctly the products from several producers. The establishment of standard
evaluation methods for photocatalytic products is therefore a challenge for
increasing their diffusion in industrial and private fields.
Japan has been a pioneer in this field, working since 2002 through the
Photocatalysis Standardization Committee dedicated to proposing standard
evaluation methods for (i) self-cleaning products; (ii) air purification products;

235
236 Chapter 8
(iii) water purification products; and (iv) antibacterial products. At present,

however, the prominent national standards bodies – European Committee for
Standardization (CEN), British Standards Institute (BSI), American Society
for Testing Materials (ASTM), Japanese Industrial Standards Committee
(JISC), etc. – are involved in proposing procedures for photocatalytic systems
evaluation.
One of the main initiatives, set to address the issue of standardization
in heterogeneous photocatalysis, is the ‘‘Photocatalytic Technologies and
Novel Nanosurfaces Materials’’ (PHONASUM) Committee founded by the
European Community. The ISO committee working on fine ceramics (TC 206)
has recently published several photocatalyst test methods, originating from the
JISC, including ones for assessing their air-purification performance via the
removal of NOx (ISO/DIS22197-1) and the measurement of water droplet
contact angle (ISO/WD 27448-1).
8.2 Efficiency Parameters of Photocatalytic Systems

8.2.1 Quantum Yield
Heterogeneous photocatalytic processes, carried out under whatever condi-
tions (suspension, film, batch or continuous), can be considered as a case of
radiative transfer in participating media and in their modeling the radiant
energy balance equation must be added to the usual equations of mass, heat
and momentum balance. The obtained set of conservation equations is very
difficult to solve because (i) the radiation field is a function of wavelength
and concentration of all the radiation absorbing species present in the par-
ticipating medium; (ii) the fluidodynamics of a fluid–solid system is highly
non-ideal so that the specific system needs to be a priori modeled; and
(iii) the kinetics of a heterogeneous photocatalytic reaction are affected in
a complex way by the concentration of the reacting species and by the
radiation field.
Provided these difficulties are overcome, the solution of conservation equa-
tions allows one to know the values of radiation intensity, temperature and
concentration of all species at each point of a reacting mixture. This infor-
mation is very valuable as it permits us to determine the parameters needed for
correctly comparing the performances of different photocatalytic systems,2 i.e.,
the rate of photon absorption (rpa) defined as:

absorbed photons einstein
rpa ¼ ð8:1Þ
ðtimeÞ ðsurface areaÞ s m2
and the intrinsic reaction rate (irr) defined as:

reacted molecules mol
irr ¼ ð8:2Þ
ðtimeÞ ðsurface areaÞ s m2
Standardization 237
The ratio between irr and rpa allows the determination of the ‘‘quantum
yield’’ (jl) for monochromatic radiation:
reacted molecules irr

jl ¼ ¼ ð8:3Þ
absorbed photons rpa
There is a general agreement in the literature that the quantum yield, a para-
meter in the form of a ‘‘number ratio,’’ is the most convenient estimator of
photocatalytic efficiency. The other parameters used for quantifying photo-
catalytic activity (such as the time needed to achieve a certain percentage of
degradation, the degradation rate, the half-life of a model compound, etc.) are
strongly dependent on the experimental conditions used so that it is difficult to
employ them for comparing different photocatalytic systems.
Importantly, even the quantum yield is not an absolute parameter. In fact in
the quantum yield definition [Equation (8.3)] both the terms of the ratio, the
rate of reaction and the rate of photon absorption, depend on intrinsic and
operative features of the photoreacting system. The reaction rate depends
heavily on parameters such as the intensity of the irradiation, the amount of the
catalyst, the nature and concentration of the reacting molecules, the con-
centration of dissolved oxygen, etc. Only for zero-order kinetics should the
reaction rate be uniquely defined at a given wavelength; often, to simplify the
evaluation, the quantum yield is based on the initial rate of molecule photo-
conversion. The absorbed photon flow depends on photoreactor geometry, the
relative position of photoreactor with respect to radiation source, the physical
and chemical characteristics of the absorbing particles, the particle agglom-
eration determined by the properties of the surrounding fluid, etc.
Proper definition of quantum yield requires careful assessment of photons
absorbed by the photocatalyst in the heterogeneous reactor. Even if the photo-
reactor set-up is standardized, the photon absorbed flow is a difficult parameter
to evaluate due to the reflection, transmission and scattering phenomena
occurring inside the photoreactor due to the presence of the semiconductor
particles.3 The extent of light scattered by the particulate matter in the dis-
persion may be very significant; according to some accounts, it may range from
20 to 80% of the total incident photon flow. Methods based on chemical
actinometry are limited as they provide only the total rate of photons entering
the reactor and do not account for various light scattering losses. In fact
semiconductor surfaces are highly reflective and therefore the light incident on
them can easily be back-scattered or forward-scattered. To overcome the dif-
ficulties encountered in the determination of the number of photons absorbed
by the photocatalyst, and given that the rate of photons entering the reactor is a
parameter much simpler to measure, researchers frequently consider an
‘‘apparent quantum yield’’ or a ‘‘photonic efficiency’’ as the parameter to be
evaluated in standardization procedures.
Photonic efficiency is defined as the number of reacting molecules divided by
the number of photons, at a given wavelength, incident inside the front window
of the cell (flat parallel windows). Given that the rate of photons entering the
238 Chapter 8
reactor is always smaller than the rate of photons absorbed, the apparent
quantum yield provides an underestimated value of the quantum yield. Even if
the photonic efficiency overcomes the difficulty of determining the absorbed
photon flow, it is a parameter that other investigators can use for comparing
their results with those of others provided that reactor geometry and light
source, together with the properties of the photocatalytic material used, are
stipulated.
To standardize the efficiencies of mineralization process of various organic
substrates for a given set of conditions, Serpone et al.4 propose to refer all
results to an equivalent experiment carried out under identical conditions for a
standard process and standard photocatalyst. The efficiency parameter used to
cross-reference the photocatalytic experiments is the ‘‘relative photonic effi-
ciency,’’ which is defined as the rate of disappearance of the substrate divided
by the rate of disappearance of a standard molecule in a standardized process.
Phenol photodegradation was suggested as the standard process and Degussa
P25 TiO2 as the standard photocatalyst. The method consists of determining
photon efficiencies by measuring the initial degradation rate of a test substrate
and the rate of photons incident on the front window of the reactor. When the
photonic efficiencies for the test substrate, and for the standard one (i.e.,
phenol), are obtained under identical experimental conditions there will be no
need to measure the absorbed photon flow. Moreover, if the quantum yield of a
standard process is determined correctly, knowledge of relative photonic effi-
ciency would allow the determination of the quantum yield of the test process.
This method has the advantage of simplicity and it overcomes all the diffi-
culties encountered in the definition of heterogeneous photocatalytic process
(determination of the absorbed photon flow, utilization of different light
sources, different reactor geometries, etc.). The main drawback of this meth-
odology is that the quantum yield of a standard process would vary enormously
with different reaction conditions, and the value would have to be determined
for each set of specific reaction conditions.
To compare different photocatalytic systems the use of quantum efficiencies
requires calculation of the incident photons in reactor media, while the use of
quantum yields requires assessment of the absorbed photons by TiO2. Quan-
tum yields and quantum efficiencies entail the implicit hypothesis that all the
energy of the used photons contributes to the formation of dOH groups.
Careful consideration of this matter is required for a proper evaluation of the
energy efficiencies.
8.2.2 Experimental Method for the Determination of Absorbed

Photons
In the absence of a solution of the integro-differential radiation transfer
equation, the photon flow absorbed by the photocatalyst particles can be
estimated by using a method reported in the literature.5–11 By considering the
scheme of Figure 8.1, the following macroscopic energy balance can be
Standardization 239
Φi
Φr
Φ'
Φa
Φt
Figure 8.1 Scheme of photon balance for a simple photoreactor.
performed on the whole suspension under the assumption that it does not lose
radiation through the lateral wall:
Fi ¼Fr þFa þFt ð8:4Þ
where Fi is the incident photon flow, Fr the backward scattered photon flow, Fa
the absorbed photon flow and Ft the transmitted photon flow.
It was found7,8 that the dependence of transmitted photon flow on mass
of catalyst is best expressed by the following relationship when the mass of
catalyst is higher than the critical one (the amount of photocatalyst sufficient
to cover the cross section of the photoreactor):
Ft ¼F0 expðEmcat Þ ð8:5Þ
where F 0 is a constant whose value is always less than that of Fi, E the napierian
extinction coefficient and mcat the mass of catalyst.
The energy balance under the limiting condition of mcat ¼ 0 allows the
determination of Fr:
Fr ¼ Fi F0 ð8:6Þ
where Fr represents the photon flow backward reflected by a medium so

optically thick that the reflectance may be hypothesized to be independent of
the medium depth, i.e., of the catalyst mass.
240 Chapter 8
8.2.3 Photochemical Thermodynamic Efficiency Factor
Serrano and De Lasa12 first introduced the ‘‘photochemical thermodynamic
efficiency factor’’ (PTEF), which evaluates the performance of a photocatalytic
system on a thermodynamic basis. A macroscopic point of view is adopted for
defining PTEF. In a photocatalytic reactor containing the irradiated catalyst a
fraction of energy emitted by the lamp is absorbed by the photocatalyst, Qabs. A
fraction of this absorbed energy is used for dOH radical formation, Qused, while
the remainder is dissipated as thermal energy and/or through parasite reactions.
The relevance of Qused and Qabs for the overall performance of photoprocess is
quantified through the definition of a dimensionless parameter, the PTEF:
Qused
PTEF ¼ ð8:7Þ
Qabs
By considering that the catalyst contained in the photoreactor consumes the

Qused energy to produce dOH radicals, the PTEF definition may be transformed
into the following:
rrad DHrad W
PTEF ¼ ð8:8Þ
Qabs
where rrad represent the formation rate of dOH radicals per unit mass of catalyst,
DHrad the formation enthalpy of an dOH radical and W the total mass of catalyst.
The PTEF is a function of the formation rate and of the formation enthalpy
of dOH radical. The latter was estimated by Serrano and de Lasa12 in aqueous
media, starting from H2O and dissolved oxygen, as 94.6 kJ mol1. Concerning
rrad, by considering that the dOH radical species is very reactive, it may be
assumed that its rate of formation is equal to its rate of consumption as
determined by the reaction with both the adsorbed model pollutant and the
adsorbed intermediates. At the very beginning of the photoconversion the
surface concentration of all chemical species equals the surface concentration of
the model compound, which acts as the only dOH scavenger; under these
conditions it may be assumed that the rate of dOH consumption is equal to the
consumption rate of model pollutant, so the following relationship holds:
rrad r0MP
¼ ð8:9Þ
vrad vMP
where r0MP represents the rate of disappearance of the model pollutant at time
t ¼ 0 (a directly measurable parameter) and nrad and nMP are the stoichiometric
coefficients for the consumption of radical and model pollutant, respectively.
The PTEF increases by increasing the initial rate of disappearance of the
model pollutant, i.e., by increasing the pollutant concentration. The driving
force of the disappearance rate of model pollutant on the catalyst surface is its
fractional site coverage, whose highest value is one. Therefore, an upper limit
Standardization 241
exists for the PTEF values; this upper value is an intrinsic characteristic of the
photodegraded pollutant as well as of the photoreactor. The PTEFmax may be
considered to be the product of two yields:
PTEFmax ¼ j0max Zrad ð8:10Þ
where j0max represents the maximum fraction of photons (absorbed by the

photocatalyst at initial conditions) that give rises to the formation of dOH
radicals, and Zrad the fraction of the photon energy used in the formation of
dOH radicals. The product of these two parameters provides an assessment of
the energy efficiency of a photoreacting system.

The PTEF is a dimensionless quantity, as required by thermodynamic
consistency; it can be broadly applied, covering various kinetic models and
being appropriate for various photochemical reactors, either homogenous or
heterogeneous.
8.2.4 Technological Parameters

A prerequisite of any technology for water cleaning is that it be able to remove
the relevant pollutant together with the conversion of total organic carbon into
inorganic carbon. The oxidation processes, including the photocatalytic ones,
must guarantee the complete mineralization of all organic carbon to insure that
the substrate(s) and any intermediate product(s) formed during the process
have also been degraded.
That prerequisite being satisfied, in selecting a specific waste-treatment
technology several important factors must be considered, such as economics,
regulations, eluent quality standards, operation etc. Among these factors eco-
nomics is generally the most important. Since photocatalytic degradation of
aqueous organic pollutants is an electric-energy intensive process (processes
under solar irradiation are not considered here), electric energy can represent a
major fraction of the operating costs.
If the efficiency of the photocatalytic process determines its economic via-
bility, the key design variables, i.e., exposure to lamp radiation and order
of magnitude of contaminant concentration removal, are combined into
parameters that for a fixed volume of contaminated water give a measure of the
treatment rate as a function of applied energy.
Two figures-of-merit are proposed:13–15 one suitable for high organic con-
centrations and the other for low concentrations. The ‘‘electric energy per
mass’’ (EEM) is defined as the electric energy required to obtain the degrada-
tion of a unit mass of a contaminant in aqueous bodies or atmosphere. The
EEM parameter is most useful when the concentration is high because under
this condition the rate of removal of the contaminant generally follows
zero-order kinetics with respect to contaminant concentration and therefore the
removal rate is directly proportional to the rate of electric energy use.
242 Chapter 8
The EEM value for a batch system can be calculated from the following
relationship:
Pt
EEM ¼ ð8:11Þ
VMðCi Cf Þ
where P is the electric power supplied to the photocatalytic system, t the

irradiation time needed to reach the desired concentration variation, V the
volume of treated water or air, M the molar mass of contaminant species and Ci
and Cf are the initial and final mass concentrations of contaminant, respec-
tively. The removal efficiencies are higher for lower EEM values.
The other figure-of-merit is the ‘‘electric energy per order’’ (EEO),14 which
is defined as the number of kWh of electrical energy required to reduce the
concentration of a pollutant species in a unit volume of contaminated water
or air by one order of magnitude (90%). The EEO parameter is best used
for low concentration values of contaminant because under this condition the
amount of electric energy required to reduce the contaminant concentration
by one order of magnitude is independent of contaminant concentration.
In fact for low contaminant concentration the degradation rate generally
follows first-order kinetics with respect to contaminant concentration and
so the time needed for any order of reduction is independent of the initial
concentration.
The EEO value for a batch system can be calculated from the following
relationship:
Pt Pt Pt
EEO ¼ ¼ ¼ ð8:12Þ
V log10 CCfi V Ci
log10 0:1C V
i
where P, t, V, Ci and Cf have the same definitions as in Equation (8.11). For

first-order kinetics the following relationship holds:

Ci Ci
ln ¼ 2:3026 log10 ¼ k1 t ð8:13Þ
Cf Cf
where k1 is the first (or pseudo-first) order rate constant for the decay of
the pollutant concentration. For a 90% variation of final concentration of
pollutant the required time of irradiation is:
2:306
t¼ ð8:14Þ
k1
Substituting Equation (8.14) into Equation (8.12) gives:
2:3026P
EEO ¼ ð8:15Þ
Vk1
Standardization 243
which is a parameter that may be easily calculated provided that the reaction
kinetics and the kWh of electricity required to reduce the pollutant con-
centration by one order of magnitude are measured.
Efficient photocatalytic processes exhibit low values of EEO, indicating that less
energy is required to achieve a fixed drop in concentration of model pollutants.
The EEO is an overall parameter based on electrical lamp power requirements
and, as such, it does not take into account the transformation efficiency of elec-
trical into useful radiative energy, radiation absorption by the photoreactor walls,
etc. Furthermore, de Lasa et al.16 outline that (i) the EEO efficiency parameter is
not dimensionless, as required by thermodynamics, (ii) the EEO definition holds
only for first-order reaction kinetics and (iii) the EEO is focused on the decrease
of the model pollutant concentration and it neglects the photoconversion of stable
intermediate species, thereby underestimating photocatalytic efficiency.
To carry out an economic analysis of various water pollutant degradation
processes, the figure of merit ‘‘energetic efficiency of degradation’’ (EED) has
been proposed.17 The EED is defined as:
parts per million of degraded organic carbon in irradiated solution
EED ¼
kWh of used electrical energy
ð8:16Þ
The EED describes the efficiency of a given process and it is a useful parameter
to determine the economic viability of different processes involving different
reactors, different light sources, etc.
In an industrial environment, process efficiencies described by EEO, EEM
and EED are useful in comparing the economics of different industrial strate-
gies. They are macroscopic parameters, which, however, do not give infor-
mation on the efficiency of an absorbed photon in inducing the photocatalytic
process, as the quantum yield does in homogeneous photochemistry and het-
erogeneous photocatalysis. Trends in EEO (or the equivalent EEM) and EED
inversely reflect the trends in quantum yields; however, they fail to provide a
relatively simple method to establish photon efficiencies.
8.3 Experimental Comparison of Photocatalytic

Systems
The photocatalytic method is capable of degrading a broad range of pollutants,
both of organic and inorganic. Therefore, several substances are suitable for
assessing the photocatalytic efficiency of a system. The literature shows that
the broad field of model pollutants and respective test procedures can be sub-
classified into three categories according to the materials used for analysis,
namely:
1. dyestuffs,18,19
2. organic compounds like volatile organic compounds (VOCs),20
3. inorganic gases.21,22
244 Chapter 8
Dyes are degraded by TiO2 under the influence of UV or solar light. The
decomposition is assessed by decolorization measurements as well as chromato-
graphic investigations. The widespread application of dyes originates from the
mainly nontoxic and convenient use of these dyes. However, the decomposition
process of dyes is still a subject of discussion as these substances only show a
limited resistance to UV light, independently of the existence of a catalyst.
Therefore, the decolorization of a dye is not an unambiguous criterion for the
assessment of photocatalytic efficiency.
VOCs are prominent representatives for modeling the degradation of pol-
luted air for indoor situations. Commonly used organic compounds are:
1. trichloroethylene (C2HCl3);23
2. acetone (C3H6O), 1-butanol (C4H10O), butyraldehyde (C4H8O) and
m-xylene (C8H10);24
3. 1,3-butadiene (C4H6) and toluene (C6H5CH3);25
4. formaldehyde (CH2O).24,25
The photocatalytic method can decompose VOCs to harmless substances like

CO2 and H2O. This also includes the removal of odors, which makes this
method especially attractive for treating air in house ventilation systems.
8.3.1 Photocatalytic Films

The activity of photocatalytic TiO2 films can vary considerably and depends on
many factors, such as film thickness, substrate, roughness, crystallite size,
deposition temperature, etc. Owing to the difficulty of defining activity para-
meters that explicitly take into account all the previous factors, it has been
proposed to standardize the photoactivity through experiments carried out
under well-defined conditions.
The experimental evaluation of photocatalytic activities of TiO2 films is
generally carried out with different methods.26 Testing methods based on the
decolorization of different dyes, such as Methylene Blue, are probably the most
commonly used as they provide an excellent visual representation of the process
evolution. In this test, a change in the color of a dye is used as an indicator of
the photocatalytic activity of the surface. In almost all cases these tests are
based upon the slow photooxidation of the dye so that they can be very long
lasting processes and therefore with limited suitability as test in the field.
Other techniques are based on the photooxidation of organic solid films such
as stearic acid deposited on the surfaces. The photocatalytic destruction of such
solid compounds is of practical interest since it represents a reasonable model
system for the type of solid organic films that are often deposited on exterior
glass surfaces. Therefore, such treatment is proposed as a standard method for
determination of activities of self-cleaning surfaces.
The drawback of all these methods is that they are not absolute methods and
a standard photocatalytic surface must be evaluated first. The relative com-
parison of the photo-efficiency of the probe to that of the standard specimen
Standardization 245
requires constant conditions. This requirement generates an important problem
as the probe conditions may differ very much between laboratories. Moreover,
many of these methods require the use of complex apparatus and as such are
suitable only for use in the laboratory, and therefore cannot be adapted to a
practical end use application.
A method recently proposed to determine the activity of photocatalytic
surfaces is based on the measurement of contact angle changes. This evaluation
method, based on ISO/TC206, consists in measuring the changes of contact
angle of a drop of distilled water put onto the TiO2 film with time under
irradiation.
8.3.1.1 Self-cleaning Glasses

An important field of successful application of photocatalytic TiO2 films is
represented by the so-called ‘‘self-cleaning’’ glasses. Thin films of anatase TiO2
deposited on glass can mineralize most of the organic pollutants present in the
atmosphere and responsible for the dirt and grime that deposit on window
glass. The TiO2 films are also hydrophilic under near-UV irradiation so that
they hinder the adhesion of hydrophobic organic pollutants to the surface
(Figure 8.2).
Comparison of the effectiveness of different self-cleaning glasses must be
made by means of standard methods capable of assessing the photocatalytic
activity. These methods should possess specific features before being adopted as
standard ones. The method should be very fast; this requirement is not easy to
accomplish because most commercial self-cleaning glasses utilize only a very
thin layer of TiO2 and therefore the photomineralization kinetics are very slow.
It can take hours or days to destroy completely a test compound under typical
solar UVA conditions.
Moreover, the method should be apt for making measurements in the field
without the need for sophisticated analytical equipment and a technician
trained to run it. The test appropriate for use in the field should involve a
simple, fast physical change, e.g., a color change within a few minutes of UV
exposure. Determination of such a set of standard methods is currently in
Figure 8.2 Self-cleaning, water-repelling glass.

246 Chapter 8
progress at the ISO (TC206). The different tests proposed and used to date are
discussed in the following.
Stearic Acid Test. The stearic acid (SA) test27–30 consists in depositing a thin
layer of SA onto the photocatalytic film under test and in monitoring
its degradation rate under strictly defined operative conditions. The dis-
appearance rate of SA is the parameter used for comparing the performances
of different samples. The stoichiometry of SA mineralization is:
TiO2
CH3 ðCH2 Þ16 COOH þ 26 O2 ! 18 CO2 þ 18 H2 O ð8:17Þ
hn
The photocatalytic mineralization of the SA film does not generate stable

intermediates, volatile or otherwise; the only major species present during the
photomineralization process being SA and CO2. Therefore, the mineraliza-
tion process can be easily monitored by following either the CO2 generation
by gas chromatography or the SA disappearance by infrared absorption
spectroscopy.
This test presents the following advantages: (i) SA may be considered as a
model compound representative of environmental contaminants forming solid
deposits on glass surfaces; (ii) SA is a very stable compound and its degradation
occurs only by photocatalysis; (iii) the deposition of a monolayer SA film from
an organic solution is very easy; (iv) because SA is a solid its concentration does
not change during degradation so that the observed kinetics are independent of
the SA film thickness; and (v) the SA degradation process is easily monitored.
Despite these very positive features, the SA test suffers from two major
drawbacks. First, with the usual thicknesses of TiO2 films deposited on glasses
(nanometer range), the test is very slow. For rapid assessment, the TiO2 films
should have a thickness in the micron range. Second, it requires a skilled
operator in both the analytical method and the sample preparation to conduct
the test, and so it is relatively labor intensive and expensive to run.
Methylene Blue Test. The Methylene Blue (MB) test31–37 is a widely used
method for assessing the photocatalytic activity of TiO2 films or powders.
MB, a cationic dye, is mineralized through a photobleaching process descri-
bed by the stoichiometry:
TiO2
2 C16 H18 N3 Sþ þ 51 O2 ! 32 CO2 þ 6 HNO3
hn ð8:18Þ
þ 2 H2 SO4 þ 2 Hþ þ 12 H2 O:
When the MB test is used for assessing photocatalytic activity, generally only
the dye decoloration, which is assumed to be due to dye oxidation, is
monitored.
Standardization 247
This method is simple, easy and able to provide an impressive demonstration
of the efficacy of semiconductor photocatalysis through dye decoloration
(Figures 8.3 and 8.4).
The main drawback of this method is that a measurable degradation of
Methylene Blue may occur38 within a few hours of UV exposure in the absence of
any catalyst. Moreover, the MB test method has been questioned39 because MB,
Figure 8.3 Methylene Blue test on un-coated and TiO2-coated solid surfaces.
(Photograph courtesy of http://www.hkapc.org/Products/TiO2)
Figure 8.4 Methylene Blue test on an aqueous TiO2 suspension. (Photograph cour-
tesy of http://www.reinbiotech.com)
248 Chapter 8
which is an indicator for redox reactions, may be easily decolorized by the
reduction reaction to leuco-Methylene Blue (LMB) which is colorless. As this
reaction is reversible, the reduced Methylene Blue can also be oxidized again and
obtain its original color. This reduction is thermodynamically possible because the
redox potentials of the MB/LMB couple and of photogenerated electrons are ca.
0.53 and 0.32 V, respectively, versus NHE at pH 0. The relative importance of MB
photooxidation with respect to photoreduction to LMB is affected by kinetic
factors. In neutral or slightly alkaline solution, the MB photobleaching is dom-
inantly determined by photooxidation. Under acidic conditions the photooxida-
tion reaction becomes slow and, as a result, the photobleaching of MB by TiO2 is
more likely to show some evidence of LMB production. MB does not work in air
since its reduced form, leuco-Methylene Blue, is highly oxygen sensitive.
Since MB shows no absolute resistance to UV-induced degradation and
decolorization by reduction reaction, it appears not to be an ideal model pol-
lutant. The ambiguity existing for the MB test must be solved before this
method of assessment can be accepted as a standard one.
Resazurin Ink Test. The major problem with the SA and MB tests is that the
photooxidation reaction is usually a slow process. Such tests are adequate
for assessing the performances of very active, usually thick, titania films,
where the kinetics of photomineralization are rapid but they are inappropri-
ate for photocatalytic products that exhibit slow degradation rates.
An innovative solution to this problem has been proposed by Mills’ research
group.40–43 The core of the test is an indicator ink that can be easily coated onto
the semiconductor film and which changes color within a few minutes upon
irradiation of the photocatalytic film.
The formulation consists of a redox dye, resazurin, a sacrificial electron donor,
glycerol, and a polymer, hydroxy ethyl cellulose, all dissolved in water. Whether
wet or dry, upon irradiation of the ink on a photocatalytic surface with ultra-
bandgap radiation the photogenerated electrons reduce the blue resazurin to the
pink resorufin (an irreversible reaction, see Figure 8.5), while the photogenerated
holes oxidize glycerol, which acts as a hole-trap preventing electron–hole
recombination, to glyceraldehyde. The reduction process is accompanied by a
color change from blue to pink; the color change indicates completion of the
photoreduction reaction and it occurs in a few minutes even for very thin TiO2
N N
hν, TiO2
Na+ -O O O Na+ -O O O
Resazurin (Rz) Resorufin (Rf)
(Blue) (Pink)
Figure 8.5 Structure of the redox dye resazurin and its reduced form, resorufin.
Standardization 249
films. The dye is stable also upon prolonged UV irradiation in the absence of a
photocatalyst; conversely, the ink changes rapidly from blue to pink upon UV
irradiation if TiO2, film or powder, is present. The process rapidity makes this test
particularly suited to ‘‘on the spot’’ tests. Moreover, this test does not need a
skilled operator or expensive analytical equipment as the eye is sufficient for a
qualitative indicator, or a semi-quantitative assessment, of photocatalytic activity.
Dichloroindophenol Test. Market research indicates that customers prefer a

decoloration test as the bleaching process is often related with a cleaning
action. The color is associated with the presence of a (contaminant) sub-
stance while the color disappearance is associated with the decontaminating
action of photocatalyst joined with light. Therefore, a photoactivity test
should involve a substance that changes from a highly colored initial form to
a colorless final form upon UV irradiation. On this basis a redox dye, i.e.,
2,6-dichloroindophenol (DCIP), has been used44 in an ink formulation in the
same manner as the resazurin ink. The resulting product arising from DCIP
reduction upon UV irradiation in the presence of a photocatalyst underlayer
is colorless, i.e., this dye is photobleached.
In a typical ink formulation, DCIP gives a blue ink and a subsequent blue
film when spun onto the surface of the photocatalyst substrate (Figure 8.6).
Although the reduction kinetics under ambient conditions for the DCIP ink are
slower than those of an resazurin ink, the latter is shown to be both oxygen and
humidity sensitive, whereas the DCIP ink is not.
Contact Angle. When a water drop lies on a solid surface, as shown in

Figure 8.7(A), the contact angle is close to 01 if the solid surface is strongly
hydrophilic. Less strongly hydrophilic solids have a contact angle up to 901.
If the solid surface is hydrophobic, the contact angle is larger than 901. A
method proposed recently to determine the activity of photocatalytic surfaces
is based on the measurement of contact angle changes by non-invasive image
sensing with a digital camera. A layer of defined thickness of oleic acid is
applied on the photocatalytic surface to be tested and then a water droplet is
placed on the surface. The water contact angle is therefore continuously
measured as a function of irradiation time by means of a computer-aided
instrument. The photocatalytic effect is determined from the time dependence
of the contact angle change and the final contact angle. The instrument is
simple, as it consists of instrument base, movable sample holder and mova-
ble digital camera with necessary electronics, and so the measurement is
quick, low cost, and easy to carry out.
8.3.2 Cementitious Building Materials

In the general field of self-cleaning surfaces a scale application of TiO2 (favored
by the relative low cost of this photocatalyst) is used in the building sector as an
250
Figure 8.6 (a) 2,6-Dichloroindophenol (DCIP) ink and (b) DCIP ink test on TiO2-coated (left-hand side) and un-coated (right hand side) solid
surfaces. (Reproduced with permission from ref. 44.)
Chapter 8
Standardization 251
Figure 8.7 (A) Contact angles, y, for (a) a hydrophobic surface, (b) a hydrophilic
surface and (c) a strongly hydrophilic surface. (B) Contact angle gonio-
meter with camera and software to capture and analyze the drop evolution
with time. [Part (A): photograph courtesy of http://harrickplasma.com.
Part (B): photograph courtesy of http://www.answers.com]
additive of cementitious materials. A European Community project (Photo-

catalytic Innovative Coverings Applications for Depollution Assessment,
PICADA) has been started with the aim of developing and testing new photo-
catalytically active building materials based on TiO2. The main result of that
project has been the development of a laboratory method able to determine the
252 Chapter 8
specific photocatalytic activity of TiO2 modified cementitious materials towards
the degradation of typical aromatic pollutants present at trace levels in indoor
and outdoor air.
In real situations the photocatalytic cementitious body is in contact through
its external surface with a gaseous body, the atmosphere, which contains
contaminant compounds at certain concentrations. Owing to the magnitude of
atmosphere with respect to the solid body it may be assumed that the con-
taminant concentration near the solid surface is constant with time and inde-
pendent of particular position on that surface. These considerations greatly
help in choosing the photoreactor to be used for characterizing the photo-
activity of cementitious materials. Generally, a continuous photoreactor (where
the catalyst is present as a fixed bed or deposited onto the reactor walls) is fed
with a gaseous stream of fixed organic vapor concentration. Measurement of
the decrease of organic vapor concentration from the inlet to the outlet of
photoreactor allows determination of the photoactivity. In these experiments, if
the conversion is high (410%), the concentration of reactants varies along the
reactor axis and then the reaction rate also varies along the axis. If the reactor is
operated at low conversion (o10%), it may be assumed that the photoreactor
behaves as a differential one, i.e., that the reactant concentrations are quite
uniform so that the photocatalytic reaction rate is determined by that con-
centration (generally the arithmetic mean between inlet and outlet). The main
drawback of differential reactors lies in the experimental errors related to
concentration measurement due to the small difference between inlet and
outlet.
A continuous stirred tank photoreactor guarantees a uniform concentration
at the sample surface. This avoids the spatial gradients of flow-through reactors
and allows high (but not very high) conversion levels (50% and over).
To measure the photocatalytic activity of TiO2 dispersed in cementitious
building materials, Strini et al.45 have developed a method based on a specially
designed stirred flow reactor. The main advantage of a mixed flow reactor is
that it allows a uniform concentration of reactants at the catalytic material
surface at high conversion factors, which also allows the photocatalytic activity
to be measured, bypassing the limitations imposed by concentration gradients
of unmixed flow reactors. During operation, following an initial equilibration
period, mainly needed for reactant adsorption on sample and on reactor sur-
faces, the system reaches steady-state conditions. The catalytic activity is cal-
culated from data measured after equilibrium has been reached. This ensures
that the resulting activity values are obtained under defined, uniform and time-
constant conditions. Under steady state conditions, all transient effects on the
sample surface and on the reactor walls are equilibrated, avoiding in this way
any interference with the determination of the catalytic activity.
A mixture of aromatic volatile organic compounds (benzene, toluene,
ethylbenzene and o-xylene, BTEX) has been chosen as a typical micropollutant
standard representative of air contamination. Because the BTEX concentration
in typical urban outdoor situations is in the 10–100 mg m3 range, BTEX
concentrations in that range must be used for the photocatalytic runs;
Standardization 253
moreover, as the humidity strongly affects the photoreactivity, the experiments
must be carried out with a water vapor content typical of outdoor situations,
e.g. 50% relative humidity (RH) at ambient temperature.
Special care must be devoted to preparation of the cementitious samples. The
specimen is prepared by mixing white cement powder with the required TiO2
amount and then adding water to the dry mixture at a fixed water/cement ratio.
The cementitious paste is manually mixed to uniformity and it is then poured
into a 9-cm diameter Petri dish filled to full height (about 1 cm). Each specimen
is allowed to hydrate for 28 days at 23 1C and a relative humidity of 495%.
After that period the specimens are exposed to 23 1C, 50% RH and allowed to
equilibrate their humidity content with the ambient air. A blank sample
without TiO2 is also prepared.
Figure 8.8 shows a schematic diagram of the experimental set-up used for
catalytic activity measurements. The system consists of an artificial atmosphere
generator system, a photochemical reactor and an irradiation box.
The atmosphere generator system uses as VOC source a standard gas
cylinder mixture containing BTEX at trace level in nitrogen. The standard
cylinder effluent stream is mixed with a humidified, oxygen-enriched synthetic
air stream. The humidification grade, oxygen level and flow of the latter are
calculated to obtain 20% oxygen, 50% RH (at 23 1C) in the air delivered to the
photocatalytic reactor.
The reaction chamber is a 2-l Duran 50 borosilicate glass (Schott) reaction
vessel provided with four service ports and a teflonated o-ring sealed cover.
Irradiation
80 ml/min box
25% O2 Solar lamp
62.5% R.H.
75% N2
Humidifier
Reactor
chamber
Inlet Outlet
sampling sampling
20 ml/min port
BTEX in N2 port Vent
Air mixing
Mass flow
controller fan Sample
GC
GC
Figure 8.8 Schematic diagram of the experimental set-up used to measure the cata-
lytic activity of cementitious materials.
254 Chapter 8
Air mixing inside the chamber is ensured by a stainless-steel fan operated
at 350 rpm. The independence of experimental BTEX concentration data from
the fan speed is verified by performing a series of measurements operating at
catalytic conditions under irradiation at different fan speeds.
The reaction chamber is contained inside an irradiation box provided with a
300 W solar lamp (Ultra Vitalux, Osram) placed 50 cm from the sample surface.
The irradiation box shields the reaction chamber from possible interference by
the ambient light, and two fans ensure reaction chamber cooling. The actual
irradiance value at the sample level is controlled for each determination,
because the lamp shows a considerable irradiation drift, particularly in the early
life period. During irradiation, the reaction chamber warms up because of the
strong visible and infrared components of the lamp radiation.
The BTEX concentration measurements are taken under steady-state con-
ditions, so it is possible to acquire multiple samples separated in time for ver-
ification and statistical data processing. The catalytic activity determination
proceeds as follows. The catalytic specimen is placed in the reaction chamber,
which is then closed inside the exposure system in dark conditions. A purified
air flow is established and maintained for 24 h, to allow possible pollutants to
be desorbed from the specimen. A first air sample is taken to check the
cleanliness of the system. The BTEX test flow is then established, connecting
the chamber to the synthetic atmosphere generator. The system is allowed to
equilibrate for at least 18 h and a series of six or more air samples are taken with
a sampling interval of at least 1 h. These samples give the non-irradiated steady-
state concentration for each VOC under study. The irradiation source is then
activated, and the system is allowed to equilibrate for at least a further 18 h. A
new series of at least six air samples are taken, giving the irradiated steady-state
concentrations. If the analyses show that the concentration is not stabilized, the
sampling is repeated after 1 day until the steady-state equilibrium is reached.
After that the lamp is turned off and, if required, the system is allowed to
re-equilibrate to the non-irradiated condition, a last sample is taken to confirm
the previously measured dark concentration levels. The BTEX concentration of
the supply air is then measured by taking a series of samples at the air inlet port
at the end of the experiment.
This photocatalytic reactor system is characterized by the specific
photocatalytic oxidation rate, measured with the following relationship:
FðCin Cirrad Þ
rox ¼ ð8:19Þ
A
where rox is the area specific oxidation rate (mmol m2 h1), F is the air
flow rate (m3 h1), Cin is the reactant concentration in the supply air flow
(mmol m3), Cirrad is the steady-state reactant concentrations in the reactor
during irradiation and A the sample area exposed to the irradiation (m2).
This method, proposed by Strini et al.,45 allows determination in a
reliable way of the surface catalytic activity in the photodestruction of
organic micropollutants in air, at ppb concentration levels. The oxidation
Standardization 255
rates of cementitious samples are linearly dependent on the air concentration
of the reactant and the catalytic activity is also linearly dependent on the
irradiation in the measured ranges. However, the catalytic activity is not
linearly dependent on the TiO2 content in the samples. Possible causes
of this are, among others, the formation of catalyst clusters in the cementitious
paste at higher concentrations or segregation processes in the poured
paste influenced by the different viscosity of the paste itself due to the presence
of the catalyst.
8.3.3 Paving Blocks

The use of organic compounds for investigating the photocatalytic properties
of cementitious materials has been questioned on the basis that during their
degradation CO2 may be produced as a consequence of mineralization. Con-
sidering the tendency of concrete to carbonation, part of this CO2 may be
transformed into solid CaCO3 in the outer pore system. Consequently, part of
the reaction products mineralize and a quantitative assessment is hampered as
the amount of mineralized CO2 consumed by carbonation is difficult to assess.
From this fact it can be concluded that the application of dyes, VOCs
and aromatic compounds is less suitable for the photocatalytic oxidation of
concrete substrates under outdoor exposure.
NOx is considered to be a suitable model pollutant for the assessment of
photocatalytic efficiency of concrete products. NOx, as also sulfur dioxide, not
only poses a threat to human health and nature preservation but it is causing
degradation to many inner-city buildings.22 A large part of the NOx in the
atmosphere is emitted by car traffic and transport. Therefore, the application of
a photocatalytic paving block (close to the source of emission) is a desirable
solution. The literature21,22 reports that the degradation of NO or more gen-
erally of NOx, also referred to as the denitrogenization process, delivers a
suitable model to assess the ability of surfaces for air purification. This deni-
trogenization process ultimately produces nitrate ions, which are flushed from
the concrete surface as weak nitric acid. Quantitative analysis of the reaction
products considering the initial pollutant concentration allows evaluation of
the degradation ability.
On the basis of the above reported considerations, NOx is a suitable model
pollutant for testing the performance of photocatalytic paving blocks. A
standard method has been proposed recently by the ISO, the ISO 22197-
1:2007;46 this test method utilizes NOx for determining the air-purification
performance shown by fine ceramics that contain a photocatalyst or have
photocatalytic films on their surface. The method consists of measuring the
photoactivity of a test piece continuously exposed to the model air pollutant
under illumination with ultraviolet light. ISO 22197-1:2007 applies to different
kinds of materials, such as construction materials in various shapes, to mate-
rials in honeycomb form and to plastic or paper materials, but only if they
contain ceramic microcrystals and composites.
256 Chapter 8
Figure 8.9 Schematic diagram of the test set-up: (1) synthetic air; (2) NOx source; (3)
gas-washing bottle; (4) temperature and relative humidity sensor; (5) flow
controller; (6) reactor cell; (7) paving block; (8) side stream for bridged
flow; (9) light source; (10) NOx analyzer; and (11) computer. (Reproduced
By considering that the standard ISO 22197-1:2007 also satisfies the need for
photoactivity measurements on concrete specimens, Hüsken et al.47 have pro-
posed an appropriate test set-up as well as a reliable measuring procedure for
determining the performance of photocatalytic active paving blocks. The used
set-up is designed by following the recommendations given by ISO 22197-
1:2007 standard and it is scaled according to the requirements on photo-
catalytic concrete products. The test set-up, which uses the UV-A induced
degradation of NO, is schematically depicted in Figure 8.9 and it consists of:
a reactor cell housing the paving block sample,

a suitable UV-A light source,
a NOx analyzer,
an appropriate gas supply.
The core of the experimental set-up is a gas reactor that allows a planar sample
of size 100 200 mm2 to be embedded. Figure 8.10 gives a schematic repre-
sentation of the reactor cell.
The reactor is made from materials that do not absorb the applied pollutant
and do not degrade under the high irradiation of UV-A light. On top, the
reactor is tightly closed with a glass plate made from borosilicate glass, which
allows the UV-A radiation to pass through with almost no absorption. Within
the reactor the planar surface of the specimen is fixed parallel to the covering
glass, leaving a 3 mm gap for the gas to pass through. The active sample area
used for the degradation process is higher than that suggested by the ISO
standard. The area is enlarged from 50 100 mm to 100 200 mm, to adjust
for the standard paving block dimensions. By means of profiles and seals, the
sample gas only passes the reactor through the gap between the sample surface
Standardization 257
Figure 8.10 Schematic diagram of the reactor cell used for the paving block test.
and the glass cover. All structural parts inside the box are designed to enable
laminar flow of the gas along the sample surface and to prevent turbulence.
The light source is chosen in order that its spectrum fits the cut-off wave-
length of the applied powder. TiO2 photocatalyst may be used as doped or
undoped powder. For undoped TiO2 the use of UV-A light is required as the
cut-off wavelength of conventional TiO2 is 388 nm;12 fluorescent tubes are
suitable lamps as they emit highly concentrated UV-A radiation in the range
300–400 nm with maximum intensity at about 345 nm. For doped powders,
having a broader spectrum covering also the visible light spectrum, standard
fluorescent lamps may be used as light source as they emit cool daylight in the
420–650 nm range with three prominent peaks at 460, 560 and 600 nm.
Warming of the reactor by the light source is prevented by the spatial
separation of light source and reactor and a cooling of the lamps by means of
fans. The irradiance of fluorescent tubes is adjusted by a dimmer to exactly
10 W m2 at the sample surface for the use of UV-A irradiation with the help of
a calibrated UV-A radiometer. A lead time of about 15 min has to be con-
sidered for fluorescent tubes to obtain a stable UV-A radiation.
As previously reported, the model pollutant chosen for conducting the
experiments on photocatalytic concrete products is NO. According to the
requirements given in standard ISO 22197-1:2007,46 the concentration of NO in
the gas feeding the photoreactor is 1 ppmv. The model contaminant, contained
in a nitrogen flow at a concentration of 50 ppmv, is mixed with synthetic air to
obtain the desired concentration and flow rate. A high precision valve is used to
adjust the concentration of the model pollutant to 1 ppmv NO. While adjusting
the concentration, the photoreactor is bypassed to avoid pollution of the
sample surface. During adjustment of the flow, the NO concentration is
monitored by the NO analyzer, connected to the outlet of the gas supply unit.
The overall gas flow rate is 16.67 cm3 s1 and the relative humidity is 50%.
258 Chapter 8
For the sake of repeatability and accuracy, a defined measuring procedure
using constant experimental conditions is also established. This procedure
distinguishes a bridged and non-bridged flow and allows therefore for a much
shorter period of adjusting the volumetric flow, pollutant concentration and
humidity. When a stable pollutant concentration is achieved, the bridge is
closed and the gas flows along the surface of the concrete sample. Initially, the
pollutant concentration decreases since the air inside the photoreactor does not
contain any NO and adsorption of NO at the sample surface takes place. After
a certain time the surface is saturated and the NO concentrations at the
photoreactor outlet and inlet show the same value.
For standard flow conditions a period of 5 min is needed to reach steady-
state conditions. At this moment, the sample is exposed to irradiation. This
leads to an immediate decrease in the NO concentration. This process of active
degradation is conducted for 30 min. Finally, the light source is switched off
and the NO concentration returns to the original inlet concentration.
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Subject Index
References to figures are given in italic type. References to tables are given in
bold type.
A*STAR 156 AirSteril purifier 214, 215

acetaldehyde 195 Airwise purifiers 217–220, 224
acetone 244 ammonia 180
adsorption 16–17 anatase 15, 43, 44
chemisorption 16–17 antibacterial coatings 107–114, 118,
desorption equilibria 20 159–160, 192, 210, 212
isotherms 17–18 anticorrosive coatings 106–107
Freundlich 17, 25–26 antireflective surfaces 102–105,
Langmuir 17, 23–25 127–129
Redlich-Peterson 26–28 arc lamps 31
photoadsorption 17–18 asphalt 151
see also superhydrophilicity atomic force microscopy
Aero Super-Element (AFM) 108–109
Purifiers 221–222
aggregate 164 bactericides see antibacterial
Ahlstrom 186, 195 coatings
Air Oasis purifiers 229–231, 230 band theory 1, 1–2
air pollution sources, vi band gap 11
air purification 98, 116–117, dopants 6–8
212–213 electronic properties 2–5
Aero Super Element 221–222 photocatalytic processes 11–16
Air Oasis 229–231, 230 photoexcitation 10–11
Airpura purifiers 226–228 redox systems 8–10
AirSteril 214, 215 surface energy 5–6
Airwise 217–220, 224 benzene 252
Comefresh 224 Bioclean Cool-Lite ST 139–140
CREC 213 bitumen 180
Daikin 215–216 bonding orbital 1
Genesis 217 brookite 43, 44, 51–52
ZAND-AIR 222–224 hydrolytic synthesis 50–51
Airpura purifiers 226–228 BTEX 252–254
Subject Index 263
building materials see cementitious dichloroindophenol test 249, 250
materials; glass dip-coating 60–64, 61
1,3-butadiene 244 Dirac constant 3
direct band gap semiconductor 3
car windshields 130 direct current magnetron
Cardinal Glass Industries 140 sputtering 75
cathode arc deposition 75–76 diuron 186, 188
cementitious materials Dives in Misericordia 151–152
glass as aggregate 164 doping 6–8, 7, 15–16, 16, 124–126,
ix 145–156, 148–149, 151–154 180
spray coating 154
standards 249–255 EcoLife homes 165–166
ceramic tiles 144, 156–162 Ecopittura/Ecopaint 156
applications 157, 158 effective mass 3
benefits 157 efficiency parameters
chemical bath deposition photochemical thermodynamic
(CBD) 80–81 efficiency factor 240–241
chemical potential 6 quantum yield 236–238
Chemical Reactor Engineering Center electric energy per mass
(CREC) 207, 213 (EEM) 241–242
chemical vapor deposition electric energy per order
(CVD) 78–80 (EEO) 242–243
chemical vapor synthesis (CVS) 78 electron beam vapor deposition 72
chemisorption 17 electron energy states 1
chloride process 45–46 electronic band theory see band
chromium 13 theory
churches 151 electrophoresis 83–84
cigarette smoke 160, 178, 195 Eley-Rideal mechanism 21
Cit de la Musique et des Beaux energetic efficiency of degradation
Arts 151 (EED) 243
colloids 155–156 energy bands see band theory
see also sol-gels Erlus Lotus 162, 163
Comefresh air purifiers 215–216, 229 Escherichia coli 107–108
concrete see cementitious materials ESSROC cement 154
conduction band 2 ethylbenzene 252
contact angle 101–102, 103, 249, 251 Ever Fine Coat 193–195
corrosion protection 106–107
cotton 178 Fermi-Dirac statistics 4
cyanide degradation 200–206 figures of merit see efficiency
parameters
Daikin air purifiers 215–216, 218 films see thin films
de Broglie relation 2 Fioravanti Hidra 130
defects 20 flame pyrolysis 46
degradation 20–22 flat band potential 9
standard tests 243–249 fluorescent lamps 31–32
Deutsche Steinzeug Cremer 156–157 inbuilt photocatalyst 231–232
264 Subject Index
fogging 117–118 ISO 22197–1:2007 255–256, 257
food packaging 113–114 isotherms of adsorption 17
formaldehyde 244 Freundlich 25–26
Freundlich isotherm 17, 25–26 Langmuir 23–25
Fujishima, Akira 156 Redlich-Peterson 26–28
Italcementi 147, 148, 152
Genesis air purifier 217, 223
Gibbs free energy 5–6 Japan Synthetic Textile Inspection
glass Institute Foundation 195
as aggregate 164
applications 117–118, 130, keratin 178, 180–182
131–140 kinetics 16–23
barrier films 120–121 adsorption 16–17
consumption rates 131 Langmuir-Hinshelwood
impurities 119–121 model 21–22
optical properties 122–123 light intensity 28–30
performance Kon Corporation 154
characterization 245–249 Kuraray Trading Company 194, 195
photocatalytic activity 123–124
polyethylene glycol 124 lamps 31–35, 208
soda-lime 118, 119 Landau-Levich equation 60–61
specifications 122–124 Langmuir isotherm 17, 23–25
Global Engineering 156 Langmuir-Hinshelwood
gold nanoparticles 180 mechanism 21
laser pyrolysis 58
HEGE Solar 102–105 lasers 32–33
Hongsheng Ceramics 162 Legionella bacteria 210, 212
hydrolytic preparation light absorption 15–16
nanostructures 49–57 light transmittance 122–123
on polymers 170 light-emitting diodes (LED) 33, 34
hydrophilicity see superhydrophilicity lipid peroxidation 107–108
Hydrotect 117, 156 liquid-solid systems 22–23
hydrothermal synthesis 49–57 low-pressure metal-organic chemical
hydroxyl radicals 29, 240 vapor deposition (LPMO
CVD) 79–80
ilmenite 45 Luch air purifiers 220–221, 225
impurities 7 lyocell fibers 183–184, 185
glass 119–121
see also doping magnetron sputtering 73–75, 172–173
incandescent lamps 32 malondialdehyde (MDA) 107
indirect band gap semiconductor 3–4 Matsushita Denso building 132
International Organization for mechanical properties
Standardization (ISO) 235 lyocell fibers 185
iron 126–127 polymers 174–175
irradiation sources see radiation Medicare Air Purifier 231
sources mercury arc lamps 31
Subject Index 265
metals 187–192 pesticide degradation 199–200, 202,
Methylene Blue 180, 244, 246–248 203
Meyerhofer equation 65 phenol 48–49
microspheres 54 Photo-CREC-Water
microwave-assisted synthesis 58–59 reactors 207–209
Millennium Inorganic Chemical photoadsorption 17–18
156 photocatalytic process 11–16
Mitsubishi Materials advantages, vii
Corporation 146–147, 148 kinetics 16–23
MOLZA Corporation 196 light dependence 28–30
multilayer films 102, 128–130, photonic efficiency 237–238
175–176 quantum yield 236–238
superhydrophilicity and 100–102
nanocrystals 46–47 photochemical thermodynamic
nanoparticles 49–50 efficiency factor (PTEF) 240–241
deposition on metals 188–189 photoexcitation 10–11, 20
nanostructures 49–57 photon absorption rate 236–237
fibers 182–183 determination 238–240
tubes 55–56 photonic efficiency 237–238
wires 56–57 photoprotection 105–106
Neat glass 140, 141 photovoltaics 102–105
Nippon Paper 219 physical vapor deposition 70–78,
Nippon Soda Corporation 191, 192 119
nitrogen oxides 144, 255 Pilkington Activ 131–135, 132, 133,
noble metals 13 136
Novosibirsk Institute of Pittsburgh Plate Glass
Catalysis 215 Company 135–137
Noxer paving blocks 145, 146 plasma deposition 75–76
plasma spray drying 68
operating rooms 112 polycarbonates 170–171, 172–173
optical properties 15–16, 122–123, poly(dimethylsiloxane-b-ether-
127–128 imide) 183
organic compounds see volatile polyethylene 175
organic compounds polyethylene oxide 183
oxidation deposition polyhedral oligosilsesquioxane
techniques 81–83 (POSS) 182–183
Oxygena tiles 160–161, 161 polymers
antimicrobial 113–114
PanaHome 165–166 applications 192–196
paper 184–187, 194, 195, 195–196 inert 172
Parylene 172 mechanical properties 174–175
patents 148–149 nanofibers 182–183
paving blocks 255–258 nanostructured coatings 177–178
see also cementitious materials spray-coating 168–169
performance characterization, poly(methyl methacrylate) 170–171,
cements 251–255 183
266 Subject Index
polymorphic forms 15–16, 42, 44 doping 6–8, 7
see also anatase; brookite; rutile photoadsorption 19–20
polytetrafluoroethylene (PTFE) 192 surface properties 4–6
poly(vinyl chloride) 175–176, 193 silica 7, 101, 120–121, 128
powders silicon nitride 121–122
preparation silver 125–126
chloride process 45–46 size-press treatment 184–185, 186
sulfate process 45 slurry reactors 202–203
preparation techniques 41, 43–49 soda-lime glass 118, 119
solvothermal preparation 57 sodium ions 119–120
suspensions 12–13 sol-gel methods 46–49, 57–58, 62,
preparation 103
films 59–70 on concrete 154–155
laser pyrolysis 58 on glass 119–120, 128–129
microwave-assisted 58–59 on metals 187–188
nanostructures 49–57 on polymers 177–178
powders 41, 43–49 on textiles 180
thin films 59–70 solar energy production 102–105
wet coating 59–70 solar radiation 34–35
propanol 63 SOLARDETOX 199
pulsed laser deposition 76–78 solvothermal synthesis 57
pumice stone 164 space-charge layer 19
purification devices see air spheroplasts 108
purification; water purification spin coating 63–67
pyrolysis spray coating
flame 46 concretes 154
laser 58 film quality 170
spray 69–70 polymers 168–169
spray pyrolysis 69–70
radiation sources 30–35 sputter deposition 72–73
intensity 28–30 stainless steel 69, 109, 111, 189–190
Raman spectroscopy 53 standards
reaction rates 28–30 cements 251–255
Redlich-Peterson isotherm 26–28 film performance 244–249
redox systems 8–11 paving blocks 255–258
reflectance 127 photochemical thermodynamic
refractive index 127 efficiency factor
resazurin ink test 248–249 (PTEF) 240–241
Rhodamine B 173–174, 175 quantum yield 236–238
rutile 15, 43, 44 water purification 241–243
standards bodies 235
Saint Gobain Glass 137–139 Staphylococcus aureus 109, 111
self-cleaning surfaces 101–102, stearic acid test 246
117–118, 130 sterilization 109–110
semiconductors sulfate process 45
band properties 2–11 Sunclean glass 135–137, 138
Subject Index 267
superhydrophilicity 18–19, 98–100, titanium isopropoxide 49–50
103, 123–124 titanium tetrachloride 49–51
films on metals 190–191 toluene 252
Pilkington Activ 132–133 TOP-NANO-HEGE coating 103
test 249 Toto Ltd. 156
surface energy 5 TPX 155–156
surface tension 5–6 transmittance (optical) 122–123
surfactants 57–58, 189–190 trichloroethylene 244
tungsten-halogen lamp 32
Taiyo Kogyo Corporation 192 TX Active cement 151–152, 152
tarpaulin 191, 192
Tedlar 172 UBE group 209–210
Temkin isotherm 17 ultraviolet irradiation 32, 33
textiles 178–184, 194 urine 160
applications 195
cotton 178–180 vacuum evaporation-deposition
thermal oxidation 81–82 70–72
thermodynamic efficiency 240–241 valence band model 1–2
thermoplastics see polycarbonates volatile organic compounds
thin films (VOC) 123–124, 243–244, 252–254,
composite 67, 102 255
deposition 59–70
cathode arc 75–76 water droplets 101–102, 103, 249, 251
chemical bath 80–81 see also superhydrophilicity
chemical vapor 79–81 water purification
electrophoretic 83–84 CREC reactors 207–209
on glass 119–120 cyanide degradation 200–206
optical properties and 127–128 fiber reactors 209–210
oxidative 81–83 pesticide degradation 199–200
physical vapor 70–78, 119 standards 241–243
pulsed laser 76–78 wave number 3
spray pyrolysis 69 wet coating technologies 59–60
sputter 72–73 dip-coating 60–64
disadvantages 42 wet-end addition 184, 186
magnetron sputtering 73–75, windshields 130
172–173
nanoparticle deposition 188–189 X-ray diffraction analysis 51–52
optical properties and 127–128 o-xylene 252
performance
characterisation 244–249 YKK Corporation 195, 196
plasma spray drying 68
on polymers 172–173 ZAND-AIR 222–224, 227
tiles see ceramic tiles zirconium dioxide 128, 129
TitanClean reflector 228

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Clean by Light Irradiation

Practical Applications of Supported TiO2

Vincenzo Augugliaro, Vittorio Loddo, Giovanni Palmisano and

r V. Augugliaro, V. Loddo, M. Pagliaro, G. Palmisano and L. Palmisano 2010

All rights reserved

Published by The Royal Society of Chemistry,

Registered Charity Number 207890

For further information see our web site at www.rsc.org

Clean by Light Irradiation: Practical Applications of Supported TiO2

Figure P.2 Air pollution sources in a house.

Figure P.3 Scheme of photocatalytic remediation.

reactions, which involve fast attack of strongly oxidant radicals, determines

Scientiﬁc and industrial interest worldwide in heterogeneous photocatalysis

Figure P.5 Superhydrophilic eﬀect.

Clean by Light Irradiation: Practical Applications of Supported TiO2

1.1.2 Properties of Semiconductor Materials

In the case of non-dispersive waves the wave number is proportional to the

where v is the propagation velocity of the wave. For electromagnetic waves

where c is the velocity of light.

Therefore, the electron momentum can be expressed as:

A semiconductor is called a direct band gap semiconductor if the energy of the

semiconductor if the minimum energy in the conduction band is shifted by a

The value of E0F is equivalent to the electrochemical potential of the electron,

Figure 1.3 Fermi–Dirac distribution for several temperatures.

where m0i is the standard chemical potential of the pure component i.

From Equation (1.17) it is possible to determine the excess concentration of a

Figure 1.4 Crystal structure of silicon.

(H+/H2) -4.5 EF 0.0 (H+/H2)

Figure 1.7 Formation of a junction between an ‘‘n’’ type semiconductor and a

(H+/H2) -4.5 EF EF,redox 0.0 (H+/H2)

When a semiconductor is irradiated by radiation of suitable energy – equal to

(a) (b) (c) (d) E (V)

corresponds to the potential of the holes. If EC is more negative than the

1.1.3 Photocatalytic Processes

-1.0 CdS CdTe CdSe

Figure 1.13 Scheme of the photocatalytic process occurring on an illuminated par-

An advantage in using semiconductor powder suspensions lies in the fact

The photocatalytic method allows, moreover, the elimination of many inor-

Figure 1.14 Photocatalytic processes in a photoelectrochemical cell (a) and on an

SC1 = CdS; WS2 SC2 = TiO2; WS3

1.2 Kinetics of Photocatalytic Processes

V ¼ k P1=n ; n41 Freundlich ð1:27Þ

where V is the volume adsorbed, Vm the volume required to form a monolayer

Figure 1.16 Photo-induced processes in a heterogeneous system containing a wide

absorption by defects generating electronically excited defects and bound and/

ASads þ Bg ! Product ð1:32Þ

The Langmuir–Hinshelwood mechanism proposes that both molecules adsorb

ASads: þ BSads: ÐProduct ð1:35Þ

A molecule adsorbs Another molecule interacts A product is formed

Two molecules adsorb They diffuse on the surface A product is formed

Figure 1.17 Graphic models of the Eley–Rideal and Langmuir–Hinshelwood

where nT is the total number of moles present in the photoreactor, nL the

where CT is the total concentration of the species and CL the concentration in

The kinetic information on a photoprocess consists of knowledge of sub-

For a batch photocatalytic runs, by hypothesizing that the main assumptions

1.2.1 Langmuir Isotherm

where K*L is the photoadsorption equilibrium constant, related to the free

Substituting in Equation (1.42) the Langmuir relationship [Equation (1.44)]