UNIT-IV

NANOMATERIALS - AN INTRODUCTION AND SYNTHETIC METHODS.

Definition of non-dimensional materials - Historical milestone - Unique properties due to
nanosize - Quantum dots. Classification of nanomaterials. General methods for the synthesis
of nanometerials - hydrothermal synthesis - solvothermal synthesis, microwave irradiation,
sol-gel and precipitation technologies, combustion flame-chemical vapour condensation
process, gas phase condensation synthesis. Reverse micelle synthesis, polymer mediated
synthesis - Protein microtube mediated synthesis. Synthesis of nanomaterials using
microorganisms and other biological agents. Sonochemical synthesis - Hydrodynamic
cavitation.

Inorganic nanomaterials - Typical examples - TiO2 /ZnO/CdO/CdS. Reactions in nanospace /

Nano-confinement/ Nano-capsules - Cavitands, Cucurbiturils, Zeolites, M.O.F.s, Pours
sillicon, nanocatalysis.

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Definition of non-dimensional materials

According to the recommendations of commission of European Union, nanomaterial

means “A natural, incidental or manufactured material containing particles, in an unbound
state or as an aggregate or as an agglomerate and where, for 50 % or more of the particles in
the number size distribution, one or more external dimensions is in the size range 1 nm - 100
nm.” A nanometer is one millionth of a millimetre approximately 100,000 times smaller than
the diameter of a human hair. In other words, nanomaterials describe, in principle, materials
of which a single unit is sized (in at least one dimension) between 1 and 1000 nanometres
(10−9 meter) but is usually 1—100 nm (the usual definition of nanoscale).

Nanomaterials are cornerstones of nanoscience and nanotechnology. Some

nanomaterials occur naturally, but of particular interest are engineered nanomaterials (EN),
which are designed for, and already being used in many commercial products and processes.
They can be found in such things as sunscreens, cosmetics, sporting goods, stain-resistant
clothing, tires, electronics, as well as many other everyday items, and are used in medicine
for purposes of diagnosis, imaging and drug delivery.

Historical Milestones of Nanomaterials

Nanostructure science and technology is a broad and interdisciplinary area of research

and development activity that has been growing explosively worldwide in the past few years.
One of the first scientific reports was the synthesis of colloidal gold particles by Michael
Faraday as early as 1857. In fact, the history of nanomaterials dates back to 1200 -1300 BC
with the discovery of soluble gold in Egypt and China. The Lycurgus cup used during 290 -
325 AD in Alexandria or Rome is another example. First book on colloidal gold by F.
Antonii was known since 1618. Book on drinkable gold that contains metallic gold in neutral
media written by J. Von Löwenstern-Kunckel from Germany was known as early as 1676.
Nanostructured catalysts have also been investigated for over 70 years. By the early
1940’s, precipitated and fumed silica nanoparticles were being manufactured and sold in
USA and Germany as substitutes for ultrafine carbon black for rubber reinforcements.
Probably most celebrated historical comment on the advancement of nanomaterials was the
public speculation by physicist Richard Feynman in 1959 about the effects of manipulating
minuscule bits of condensed matter in his famous talk “There’s plenty of room at the
bottom”.

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 In the 1960s and 1970s metallic nanopowders for magnetic recording tapes were
developed. In 1976, for the first time, nanocrystals produced by the now popular inert- gas
evaporation technique was published by Granqvist and Buhrman. Recently it has been found
that the Maya blue paint is a nanostructured hybrid material. The origin of its color and its
resistance to acids and bio corrosion are still not understood but studies of authentic samples
from Jaina Island show that the material is made of needle-shaped palygorskite (clay) crystals
that form a super lattice with a period of 1.4 nm, with intercalates of amorphous silicate
substrate containing inclusions of metal (Mg) nanoparticles. The beautiful tone of the blue
color is obtained only when both these nanoparticles and the super lattice are present, as has
been shown by the fabrication of synthetic samples.
In 1986, a very-high-resolution type of scanning probe microscopy invented, it more
than 1000 times better than the optical diffraction limit. The scientists in IBM Almaden
Research Center in San Jose, California, of the used a scanning tunneling microscope to
position 35 individual xenon atoms on a substrate of chilled crystal of nickel to form the
acronym "IBM". They also created chains of xenon atoms similar in form to molecules in
1989. In 1991, after the discovery and verification of the fullerenes, Sumio Iijima of NEC
observed multiwall nanotubes formed in a carbon arc discharge, and two years later, he and
Donald Bethune at IBM independently observed single-wall nanotubes – buckytubes. These
pure carbon polymers could now be understood in the context of fullerenes, changing the
perception of them to molecules, with all that special designation implies. Nanotubes had
been fullerenized. Zyvex was founded in 1997, as the first molecular nanotechnology
company, with the vision of developing atomically precise manufacturing. President
Clinton’s FY 2001 budget request includes a $227 million (84%) increase in the
government’s investment in nanotechnology research and development. The Administration
is making this major new initiative, called the National Nanotechnology Initiative (NNI), a
top priority. This was followed by 21st Century Nanotechnology Research and Development
Act, USA in the year 2003. Further, more an action plan on nanosciences and
nanotechnologies was devised in Europe in the year 2005.
Today nanophase engineering expands in a rapidly growing number of structural and
functional materials, both inorganic and organic, allowing manipulation of mechanical,
catalytic, electric, magnetic, optical and electronic functions. The production of nanophase or
cluster-assembled material is usually based upon the creation of separated small clusters
which then are fused into a bulk-like material or on their embedding into compact liquid or
solid matrix materials. The nanophase silicon, which differs from normal silicon in physical

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and electronic properties, could be applied to macroscopic semiconductor processes to create
new devices. Similarly when ordinary glass is doped with quantized semiconductor
''colloids,'' it becomes a high performance optical medium with potential applications in
optical computing.
In the year 2016 Nobel Prize for Chemistry has been awarded to a trio of
scientists for their pioneering work in developing nano-molecular machines. These
gadgets measure just a thousandth of a human hair in width, and they’re poised to
revolutionize everything from manufacturing and materials to medicine and the
functioning of the human body. The winners of this year’s prize are Jean-Pierre
Sauvage from the University of Strasbourg, France, Sir J. Fraser Stoddart from
Northwestern University in Illinois, and Bernard L. Feringa from the University of
Groningen in the Netherlands.

Unique Properties of Nanomaterials

Nanomaterials are of interest because of its scale and unique optical, magnetic,
electrical, and other properties emerge. They are a link between bulk materials and atomic or
molecular structures. While bulk materials have constant physical properties regardless of its
size, among nanoparticles the size often dictates the physical and chemical properties. Thus,
the properties of materials change as their size approaches the nanoscale and as the
percentage of atoms at the surface of a material becomes significant. For bulk materials, those
larger than one micrometer (or micron), the percentage of atoms at the surface is insignificant
in relation to the number of atoms in the bulk of the material.

The two main reasons why materials at the nano scale can have different properties
are increased relative surface area and new quantum effects. Nanomaterials have a much
greater surface area to volume ratio than their conventional forms, which can lead to greater
chemical reactivity and affect their strength. Also at the nano scale, quantum effects can
become much more important in determining the materials properties and characteristics,
leading to novel optical, electrical and magnetic behaviours.

Physical properties of nanoparticles

Nanoparticles are unique because of their large surface area and this dominates the
contributions made by the small bulk of the material. For example, zinc oxide particles have
been found to have superior UV blocking properties compared to its bulk substitute. This is
one of the reasons why it is often used in the preparation of sunscreen lotions.

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Other examples of the physical properties of nanoparticles:

 Coloured nanoparticles of yellow gold and gray silicon are red in color

 Gold nanoparticles melt at much lower temperatures (~300 °C for 2.5 nm size) than
the gold slabs (1064 °C)

 Absorption of solar radiation in photovoltaic cells is much higher in nanoparticles than

it is in thin films of continuous sheets of bulk material (since the particles are smaller),
they absorb greater amount of solar radiation

Optical properties of nanoparticles are unique. Nanoparticles also often possess

unexpected optical properties as they are small enough to confine their electrons and produce
quantum effects. One example of this is that gold nanoparticles appear deep red to black in
solution.

Formation of suspensions. An important physical property of nanoparticles is their

ability to form suspensions. This is possible since the interaction of the particle surface with
the solvent is strong enough to overcome density differences. In bulk materials this
interactions usually result in a material either sinking or floating in a liquid.

Magnetization and other properties of nanoparticles. Other properties unique

among nanoparticles are quantum confinement in semiconductor particles, surface plasmon
resonance in some metal particles and super-paramagnetism in magnetic materials. For
example, ferroelectric materials smaller than 10 nm can switch their magnetisation direction
using room temperature thermal energy, thus making them unsuitable for memory storage.
Thus this property is not always desired in nanoparticles.

Diffusion properties of nanoparticles. At elevated temperatures especially,

nanoparticles possess the property of diffusion. Sintering can take place at lower
temperatures, over shorter time scales than for larger particles. Although this does not affect
the density of the final product but there is a chance of agglomeration.

Hardness of nanoparticles. Clay nanoparticles, when incorporated into polymer

matrices, increase reinforcement, leading to stronger plastics. These nanoparticles are hard,
and impart their properties to the polymer (plastic). Nanoparticles have also been attached to
textile fibers in order to create smart and functional clothing.

Semisolid or soft nanoparticles. Semi-solid and soft nanoparticles have been

manufactured. Notable of these is the liposome. Various types of liposome nanoparticles are

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currently used clinically as delivery systems for anticancer drugs, antibiotics and antifungal
drugs and vaccines.

Dimensionality. Nanoparticles are generally classified based on their dimensionality,

morphology, composition, uniformity, and agglomeration. They can have 0, 1, 2 and 3
dimension and the details are discussed under the title classification of nanomaterials.
Nanomaterials have created a high interest in recent years by virtue of their unusual
mechanical, electrical, optical and magnetic properties. The range of commercial
nanomaterials available today is very broad, including stain-resistant and wrinkle-free
textiles, cosmetics, sunscreens, electronics, paints and varnishes. Nano-coatings and nano-
composites are finding uses in diverse consumer products, such as windows, sports
equipment, bicycles and automobiles. There are novel UV-blocking coatings on glass bottles
which protect beverages from damage by sunlight, and longer-lasting tennis balls using
butylrubber/ nano-clay composites. Nanoscale titanium dioxide, for instance, is finding
applications in cosmetics, sun-block creams and self-cleaning windows, and nanoscale silica
is being used as filler in a range of products, including cosmetics and dental fillings.
Nanophase ceramics are of particular interest because they are more ductile at elevated
temperatures as compared to the coarse-grained ceramics.
Nanostructured metal clusters and colloids of mono- or plurimetallic composition
have a special impact in catalytic applications. They may serve as precursors for new type of
heterogeneous catalysts (Cortex-catalysts) and have been shown to offer 1.6 Introduction to
Nanomaterials substantial advantages concerning activity, selectivity and lifetime in chemical
transformations and electrocatalysis (fuel cells). Enantioselective catalysis was also achieved
using chiral modifiers on the surface of nanoscale metal particles. Polymer based composites
with a high content of inorganic particles leading to a high dielectric constant are interesting
materials for photonic band gap structure.

Quantum dots

Quantum dots (QDs) are tiny crystals that have special properties due to their size and
chemical makeup. Quantum dots are only about 1/10,000th the width of a human hair, and
contain several hundred to several thousand atoms, depicted as different coloured spheres in
the image below. The structure of a quantum dot plays an important role in its properties
(Figure 1).

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 Figure 1 The physical structure of quantum dots

QDs can be optically excited. However, a lot of physics behind those properties still
remain unknown. On absorbing photons, electrons in QDs gain energy leading to the creation
of excitons. An exciton is a bound state of an electron and a quasi particle called a hole. After
relaxation from the excitonic excited state to its lower energy state, the electron and hole
recombine (exciton recombination), emitting a photon. The overall process of optical
excitation, relaxation of excited state, recombination of electron and hole and fluorescent
emission is called photoluminescence (PL). The number of photons emitted can be measured
as a function of energy, which gives the PL spectrum.

Fluorescent resonant energy transfer (FRET) is a very common separation dependent

phenomenon among many dyes. The unique properties of QDs make them ideal FRET pair.
By measuring the separation dependent FRET level between QDs, one can discover the
physics behind this phenomenon: whether the interaction is dipole-dipole or dipole-
quadrapole dependence, which is an interest physics topic to be explored. If the separation
dependence interaction is well controlled, it is highly possible to make QDs as a “calibrated”
nano-scale ruler for potential biology application.

The energy gap of excitons in QDs is strongly size dependent. This size dependent
phenomenon is due to the effect of confinement: The smaller QDs have stronger confinement
making the energy gap larger. Similarly, a larger size gives a smaller energy gap. Hence, QDs
with different emission colours can be made from the same material by changing their size.
Colloidal QDs, which are synthesized by relatively inexpensive wet chemistry methods,
make it possible to have the desired particle size which makes it easy to find QDs with the

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energy spectrum we need and high quantum yield (number of photons absorbed over the
number of photons emitted), even at room temperature. Currently, CdSe or CdTe QDs with a
ZnS shell are commonly used and studied. The Core/Shell structure diminishes chemical
damage to the fluorescence core. ZnS is optically transparent to the emission range, therefore
there are no photon losses associated to the shell with visible light emission.

Different from many organic dyes, the emission light spectra of QDs are narrower and
more symmetric than conventional organic dyes, making the sensitivity of detection higher
than for organic dyes. Because of this property, QDs are attractive fluorophores for biological
imaging (biological tagging), useful materials in the electronics, medical and other industries.
In the display and lighting industries, these properties are harnessed to generate vivid colours
with low power consumption for mobile phones, televisions, and general lighting so the
consumer benefits from longer battery life, beautiful pictures and video, and a lower
electricity bill.

Classification of Nanomaterials
Nanomaterials can be categorized based on dimensions, origin and their structural
configuration.
Classification based on the dimensions
Siegel classified nanomaterials based on the dimensions as zero dimensional, one
dimensional, two dimensional and three dimensional nanostructures (Figure 2). Which are
characterized by an ultra fine grain size (< 50 nm) or by a dimensionality limited to 50 nm.

Figure 2 Classification of Nanomaterials (a) 0D spheres and clusters, (b) 1D nanofibers,

wires, and rods, (c) 2D films, plates, and networks, (d) 3D nanomaterials.

a) Zero dimensional (0-D) nanomaterials: These nanomaterials have nano-dimensions in

all the three directions. Metallic nanoparticles including gold and silver nanoparticles and
semiconductor such as quantam dots are the perfect example of this kind of nanoparticles.
Most of these nanoparticles are spherical in size and the diameter of these particles will be

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 in the1-50 nm range. Cubes and polygons shapes are also found for this kind of
nanomaterials. Zero dimensional Nanoparticles can be amorphous or crystalline, single
crystalline or polycrystalline, composed of single or multi-chemical elements, exhibit
various shapes and forms, exist individually or incorporated in a matrix, be metallic,
ceramic, or polymeric.
b) One dimensional (1-D): In these nanostructures, one dimension of the nanostructure
will be outside the nanometer range. These include nanowires, nanorods, and nanotubes.
These materials are long (several micrometer in length), but with diameter of only a few
nanometer. Nanowire and nanotubes of metals, oxides and other materials are few
examples of this kind of materials. One dimensional nanoparticles can be amorphous or
crystalline, single crystalline or polycrystalline, chemically pure or impure, standalone
materials or embedded in within another medium, metallic, ceramic, or polymeric.
c) Two dimensional (2-D): In this type of nanomaterials, two dimensions are outside the
nanometer range. These include different kind of nano films such as coatings and thin-
film-multilayers, nano sheets or nano-walls. The area of the nano films can be large
(several square micrometer), but the thickness is always in nano scale range. Two
dimensional nanoparticles can be amorphous or crystalline, made up of various chemical
compositions, used as a single layer or as multilayer structures, deposited on a substrate,
integrated in a surrounding matrix material, metallic, ceramic, or polymeric.
d) Three Dimensional (3-D): All dimensions of a three dimensional material are outside
the nano meter range. These include bulk materials composed of the individual blocks
which are in the nanometer scale (1-100 nm). Three dimensional nanoparticles can contain
dispersions of nanoparticle, bundles of nanowires, and nanotubes as well as
multinanolayers.
Classification based on their origin
i) Natural nanomaterials: Nanomaterials which are belonging to resource of nature are
defined as natural nanometer. Virus, protein molecules including antibody originated from
nature are some natural nano structured materials. In addition following are few examples,
mineral such as clays, natural colloids, such as milk and blood (liquid colloids), fog (aerosol
type), gelatine (gel type), mineralised natural materials, such as shells, corals and bones,
insect wings and opals, spider silk, lotus leaf, Gecko feet, volcanic ash, ocean spray, etc.

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ii) Artificial nanomaterial: Artificial nanoparticles are those which are prepared deliberately
through a well-defined mechanical and fabrication process. The examples of such materials
are carbon nanotubes, semiconductor nanoparticles like quantum dots etc.

Classification based on structural configuration

i) Carbon based nano-materials: The nature of this kind of nanomaterials is hollow spheres,
ellipsoids, or tubes. Spherical and ellipsoidal configured carbon nanomaterials are defined as
fullerenes, while cylindrical ones are described as nanotubes.

ii) Metal Based Materials: The main component of these particles is metal. These
nanomaterials include nanogold, nanosilver and metal oxides, such as titanium dioxide and
closely packed semiconductor like quantum dots.

iii) Dendrimers: Dendrimers are highly branched macromolecules with the dimensions
nanometer-scale. The surface of a dendrimer posses numerous chain which can be modified
to perform specific chemical functions. PAMAM dendrimer is the best illustration of this
kind of materials.

iv) Composites: Nanocomposite can be described as a multiphase solid material where at

least one of the phases has one, two or three dimensions in nanoscale. The most common
examples of these materials are colloids, gels and copolymers.

Examples of Nanomaterials
Nanomaterials (gold, carbon, metals, meta oxides and alloys) with variety of
morphologies (shapes) are depicted in Figure 3.

Figure 3 Examples of nanomaterials

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Nanomaterial - Synthesis and Processing
There are many different ways of creating nanostructures. Macromolecules or
nanoparticles or bucky balls or nanotubes and so on can be synthesized artificially for certain
specific materials. They can also be arranged by methods based on equilibrium or near-
equilibrium thermodynamics such as methods of self-organization and self-assembly
(sometimes also called bio-mimetic processes). Using these methods, synthesized materials
can be arranged into useful shapes so that finally the material can be applied to a certain
application.

Hydrothermal synthesis

Hydrothermal synthesis includes the various techniques of crystallizing substances

from high-temperature aqueous solutions at high vapor pressures; also termed "hydrothermal
method". The term "hydrothermal" is of geologic origin. Hydrothermal synthesis can be
defined as a method of synthesis of single crystals that depends on the solubility of minerals
in hot water under high pressure. The crystal growth is performed in an apparatus consisting
of a steel pressure vessel called an autoclave, in which a nutrient is supplied along with water.
A temperature gradient is maintained between the opposite ends of the growth chamber. At
the hotter end the nutrient solute dissolves, while at the cooler end it is deposited on a seed
crystal, growing the desired crystal.

Advantages of the hydrothermal method over other types of crystal growth include the
ability to create crystalline phases which are not stable at the melting point. Also, materials
which have a high vapour pressure near their melting points can be grown by the
hydrothermal method. The method is also particularly suitable for the growth of large good-
quality crystals while maintaining control over their composition. Disadvantages of the
method include the need of expensive autoclaves, and the impossibility of observing the
crystal as it grows.

Uses: A large numbers of compounds belonging to practically all classes have been
synthesized under hydrothermal conditions, elements, simple and complex oxides, tungstates,
molybdates, carbonates, silicates, germanates etc. Hydrothermal synthesis is commonly used
to grow synthetic quartz, gems and other single crystals with commercial value. Some of the
crystals that have been efficiently grown are emeralds, rubies, quartz, alexandrite and others.
The method has proved to be extremely efficient both in the search for new compounds with

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specific physical properties and in the systematic physicochemical investigation of intricate
multi-component systems at elevated temperatures and pressures.

Solvothermal synthesis

Solvothermal synthesis is a method of producing chemical compounds. It is very

similar to the hydrothermal route (where the synthesis is conducted in a stainless steel
autoclave), the only difference being that the precursor solution is usually not aqueous
(however, this is not always the case in all literature uses of the expression (Figure 3). Using
the solvothermal route gains one the benefits of both the sol-gel and hydrothermal routes.
Thus solvothermal synthesis allows for the precise control over the size, shape distribution,
and crystallinity of metaloxide nanoparticles or nanostructures. These characteristics can be
altered by changing certain experimental parameters, including reaction temperature, reaction
time, solvent type, surfactant type, and precursor type. Solvo-thermal synthesis has been used
in laboratory to make nano structured titanium dioxide, graphene,carbon and other materials.

Figure 3 Schematic diagram of solvo-thermal synthesis setup. 1. stainless steel autoclave, 2.

precursor solution, 3. teflon liner, 4. stainless steel lid.

Microwave irradiation

Various TiO2 nanomaterials materials have been synthesised using microwave radiation.
Microwave techniques eliminate the use of high temperature calcination for extended periods of
time and allow for fast, reproducible synthesis of crystalline TiO2 nanomaterials (Figure 4). High
quality rutile rods were developed combining hydrothermal and microwave synthesis, while TiO2
hollow, open ended nanotubes were synthesised through reacting anatase and rutile crystals in
NaOH solution.

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Figure 4 Drawing of two extremes of microwave-assisted reactions. The vial on the left
contains a solution with a large tan (such as water). Upon microwave irradiation, the
microwaves minimally penetrate the reaction volume due to efficient absorption by the
solvent.

Sol-gel process

The sol-gel process, involves the evolution of inorganic networks through the
formation of a colloidal suspension (sol) and gelation of the sol to form a network in a
continuous liquid phase (gel). The precursors for synthesizing these colloids consist usually
of a metal or metalloid element surrounded by various reactive ligands (Figure 5). The
starting material is processed to form a dispersible oxide and forms a sol in contact with
water or dilute acid. Removal of the liquid from the sol yields the gel, and the sol/gel
transition controls the particle size and shape. Calcination of the gel produces the oxide.
Sol-gel processing refers to the hydrolysis and condensation of alkoxide-based
precursors such as Si(OEt)4 (tetraethyl orthosilicate, or TEOS). The reactions involved in the
sol-gel chemistry based on the hydrolysis and condensation of metal alkoxides M(OR)z can
be described as follows:
MOR + H2O → MOH + ROH (hydrolysis)
MOH + ROM → M-O-M + ROH (condensation)
Sol-gel method of synthesizing nanomaterials is very popular amongst chemists and is
widely employed to prepare oxide materials. The sol-gel process can be characterized by a
series of distinct steps.

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 Figure 5 Schematic representation of sol-gel process of synthesis of nanonaterial.
a. Formation of different stable solutions of the alkoxide or solvated metal precursor.
b. Gelation resulting from the formation of an oxide- or alcohol- bridged network (the gel) by
a polycondensation reaction that results in a dramatic increase in the viscocity of the solution.
c. Aging of the gel (Syneresis), during which the polycondensation reactions continue until
the gel transforms into a solid mass, accompanied by contraction of the gel network and
expulsion of solvent from gel pores. Ostwald ripening (also referred to as coarsening, is the
phenomenon by which smaller particles are consumed by larger particles during the growth
process) and phase transformations may occur concurrently with syneresis. The aging process
of gels can exceed 7 days and is critical to the prevention of cracks in gels that have been
cast.
d. Drying of the gel, when water and other volatile liquids are removed from the gel network.
This process is complicated due to fundamental changes in the structure of the gel. The
drying process has itself been broken into four distinct steps: (i) the constant rate period, (ii)
the critical point, (iii) the falling rate period, (iv) the second falling rate period. If isolated by
thermal evaporation, the resulting monolith is termed a xerogel. If the solvent (such as water)
is extracted under supercritical or near super critical conditions, the product is an aerogel.
e. Dehydration, during which surface- bound M-OH groups are removed, there by stabilizing
the gel against rehydration. This is normally achieved by calcining the monolith at
temperatures up to 8000 oC.
f. Densification and decomposition of the gels at high temperatures (T > 8000 oC). The pores
of the gel network are collapsed, and remaining organic species are volatilized.
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 Interest in this synthetic method arises due to the possibility of synthesizing non metallic
inorganic materials like glasses, glass ceramics or ceramic materials at very low temperatures
compared to the high temperature process required by melting glass or firing ceramics. The
major difficulties to overcome in developing a successful bottom-up approach is controlling
the growth of the particles and then stopping the newly formed particles from agglomerating.
Other technical issues are ensuring the reactions are complete so that no unwanted reactant is
left on the product and completely removing any growth aids that may have been used in the
process. Also production rates of nano powders are very low by this process. The main
advantage is one can get monosized nano particles by any bottom up approach.

Chemical Vapour Condensation (CVC)

As shown schematically in figure 6, the evaporative source used in Gas Condensation
Processing (GPC) is replaced by a hot wall reactor in the Chemical Vapour Condensation or
the CVC process. Depending on the processing parameters nucleation of nanoparticles is
observed during chemical vapour deposition (CVC) of thin films and poses a major problem
in obtaining good film qualities. The original idea of the novel CVC process which is
schematically shown below where, it was intended to adjust the parameter field during the
synthesis in order to suppress film formation and enhance homogeneous nucleation of
particles in the gas flow. It is readily found that the residence time of the precursor in the
reactor determines if films or particles are formed. In a certain range of residence time both
particle and film formation can be obtained.

Figure 6 Schematic representation of chemical vapour deposition

Adjusting the residence time of the precursor molecules by changing the gas flow
rate, the pressure difference between the precursor delivery system and the main chamber
occurs. Then the temperature of the hot wall reactor results in the fertile production of
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nanosized particles of metals and ceramics instead of thin films as in CVD processing. In the
simplest form a metal organic precursor is introduced into the hot zone of the reactor using
mass flow controller. Additionally, more complex oxides such as BaTiO3 or composite
structures can be formed as well. Appropriate precursor compounds can be readily found in
the CVD literature. The extension to production of nanoparticles requires the determination
of a modified parameter field in order to promote particle formation instead of film
formation. In addition to the formation of single phase nanoparticles by CVC of a single
precursor the reactor allows the synthesis of
1. mixtures of nanoparticles of two phases or doped nanoparticles by supplying two
precursors at the front end of the reactor, and
2. coated nanoparticles, i.e., n-ZrO2 coated with n-Al2O3 or vice versa, by supplying a
second precursor at a second stage of the reactor. In this case nanoparticles which have
been formed by homogeneous nucleation are coated by heterogeneous nucleation in a
second stage of the reactor. Figure 6 shows schematic representation of CVC reactor.
Because, CVC processing is continuous, the production capabilities are much larger
than in GPC processing. Quantities in excess of 20 g/hr have been readily produced with a
small scale laboratory reactor. A further expansion can be envisaged by simply enlarging the
diameter of the hot wall reactor and the mass flow through the reactor.

Gas Condensation Processing (GPC)

In this technique, a metallic or inorganic material, e.g. a suboxide, is vaporised using

thermal evaporation sources such as crucibles, electron beam evaporation devices or
sputtering sources in an atmosphere of 1-50 mbar He (or another inert gas like Ar, Ne, Kr).
Cluster form in the vicinity of the source by homogenous nucleation in the gas phase and
grow by coalescence and incorporation of atoms from the gas phase (Figure 7). The cluster or
particle size depends critically on the residence time of the particles in the growth system and
can be influenced by the gas pressure, the kind of inert gas, i.e. He, Ar or Kr, and on the
evaporation rate/vapour pressure of the evaporating material. With increasing gas pressure,
vapour pressure and mass of the inert gas used the average particle size of the nanoparticles
increases. Log normal size distributions have been found experimentally and have been
explained theoretically by the growth mechanisms of the particles. Even in more complex
processes such as the low pressure combustion flame synthesis where a number of chemical
reactions are involved the size distributions are determined to be lognormal.

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Figure 7 Schematic representation of typical set-up for gas phase condensation synthesis of
nanomaterials followed by consolidation in a mechanical press or collection in an appropriate
solvent media.
Originally, a rotating cylindrical device cooled with liquid nitrogen was employed for
the particle collection: the nanoparticles in the size range from 2-50 nm are extracted from
the gas flow by thermophoretic forces and deposited loosely on the surface of the collection
device as a powder of low density and no agglomeration. Subsequently, the nanoparticles are
removed from the surface of the cylinder by means of a scraper in the form of a metallic
plate. In addition to this cold finger device several techniques known from aerosol science
have now been implemented for the use in gas condensation systems such as corona
discharge, etc. These methods allow for the continuous operation of the collection device and
are better suited for larger scale synthesis of nanopowders. However, these methods can only
be used in a system designed for gas flow, i.e. a dynamic vacuum is generated by means of
both continuous pumping and gas inlet via mass flow controller. A major advantage over
convectional gas flow is the improved control of the particle sizes. It has been found that the
particle size distributions in gas flow systems, which are also lognormal, are shifted towards
smaller average values with an appreciable reduction of the standard deviation of the
distribution. Depending on the flow rate of the He gas, particle sizes are reduced by 80% and
standard deviations by 18%.

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 The synthesis of nanocrystalline pure metals is relatively straightforward as long as
evaporation can be done from refractory metal crucibles (W, Ta or Mo). If metals with high
melting points or metals which react with the crucibles, are to be prepared, sputtering, i.e. for
W and Zr, or laser or electron beam evaporation has to be used. Synthesis of alloys or
intermetallic compounds by thermal evaporation can only be done in the exceptional cases
that the vapour pressures of the elements are similar. As an alternative, sputtering from an
alloy or mixed target can be employed. Composite materials such as Cu/Bi or W/Ga have
been synthesised by simultaneous evaporation from two separate crucibles onto a rotating
collection device. It has been found that excellent intermixing on the scale of the particle size
can be obtained. However, control of the composition of the elements has been difficult and
reproducibility is poor. Nanocrystalline oxide powders are formed by controlled post
oxidation of primary nanoparticles of a pure metal (e.g. Ti to TiO2) or a suboxide (e.g. ZrO to
ZrO2). Although the gas condensation method including the variations have been widely
employed to prepared a variety of metallic and ceramic materials, quantities have so far been
limited to a laboratory scale. The quantities of metals are below 1 g/day, while quantities of
oxides can be as high as 20 g/day for simple oxides such as CeO2 or ZrO2. These quantities
are sufficient for materials testing but not for industrial production. However, it should be
mentioned that the scale-up of the gas condensation method for industrial production of
nanocrystalline oxides by a company called nanophase technologies has been successful.

Reverse Micelle Synthesis

The reverse micelles can be used as templates for the synthesis of inorganic
nanomaterials by precipitation technique. This technique enables nano-precipitation of the
materials such as metal, semiconductor, metal oxide and insoluble salt nanoparticles. When
the precipitation is carried out in an aqueous medium, the rate of precipitation is too rapid to
allow fine control of the particle size. Further, the distribution of particle size is quite wide.
The particles generated by the conventional precipitation techniques are generally isotropic in
properties as there is no control of particle shape. Therefore, there is a need for a technique
which will enable precise control of particle size, its distribution and shape. Reverse miceller
colloidal precipitation fulfils this need.
Amphiphilic surfactant molecules when present in an organic solvent form reverse
micelles hence the surfactant concentration exceeds a certain critical value known as the
critical micelle concentration (CMC). Reverse micelles are self assembled nanostructures
with hydrophilic heads of surfactant molecules oriented inwards and hydrophobic tails

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outwards in the organic solvent matrix (Figure 8). These micelles can be spherical,
cylindrical or lamellar depending upon the type and amount of the surfactant. These reverse
micelles permit formation of ‘water-in-oil’ emulsion wherein small water droplets are
embedded inside the reverse micelle. The size of the droplet can be controlled by the amount
of water present (Droplet size control).
These water droplets undergo Brownian motion which results into their collision
accompanied by the mixing and exchange of water among the droplets. The droplets of
original size are reformed. (Water exchange process). When two different colloidal solutions,
each with an individual reactant in their reverse micelles, are mixed, the precipitation reaction
occurs in the micelle. The nanoparticles thus get formed. The size of the particle is confined
by the size of the micelle which is of the order of few nanometers.

Figure 8 A drawing of (a) a reverse micelle and (b) a more realistic model of reverse micelle.
Thus, the reverse micelle formation, droplet size control and water exchange are the
three key processes in nanoparticle formation by the reverse miceller technique. This
technique can be employed for the following type of reactions:
1. Precipitation by double decomposition: Synthesis of silver halide nano particles from silver
nitrate and sodium halide reverse micelles
2. Reduction: Metal nanoparticles like iron, silver, copper, zinc can be made starting with
their divalent surfactants [M(AOT)2] and a reductant like hydrazine.
3. Hydrolysis followed by condensation: Metal oxides like vanadium pentoxide can be
synthesized starting with alkoxides dissolved in organic phase and hydrolysis taking place in
aqueous micelle.
Polymer Mediated Synthesis
Polymer mediated nanoparticles represent one of most the important nanomaterials in
current nanotechnology. Polymer self-assembly of nanoparticles yields stabilized metal and
semiconductor nanocomposites as well as provides access to structured nanoscale materials.

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The properties of these materials can be tuned by varying the size and shape of the metal
cluster as well as by altering the composition of the monolayer that covers the particles.
Furthermore, the functionality and structure of the polymer can be modified, which lends an
additional element of control to the entire assembly process. This ”bottom-up” approach
provides a methodology that is complementary to ”top-down” lithographic methods,
providing access to structures smaller and with greater 3-dimensional (3-D) control than is
possible through sophisticated lithographic techniques such as electron-beam lithography.

Monodisperse polymer-mediated platinum (Pt) nanoparticles could be synthesized by

photoreduction in the presence of polyethylenimine (PEI), a hyperbranched polymer. The
photoreduction of Pt complexes is an attractive method because,

 large number of platinum nuclei are homogeneously and instantaneously produced, so the
reduction reaction arises uniformly performed in the solution, thus the size of final
nanoparticles is very uniform.
 Controlled reduction of metal ions can be carried out without using excess reducing agent,
and no adsorbing contamination on the product occurs in the preparation process.
 The photochemical method can be cost-effective and convenient.

It involves reduction of platinum ions into nanoparticles in protective media to

prevent the metal nanoparticles from aggregating. Water soluble polymers such as poly(vinyl
alcohol) (PVA) and poly(N-vinyl-2-pyrrolidone) (PVP) have been widely used as protective
media for colloidal dispersions. Stabilizers play an important role in controlling the formation
of nanoparticles as well as their dispersion stability. On the other hand the presence of too
strong capping agents on the nanoparticles surfaces can produce a detrimental impact on the
particle’s catalytic properties. For example, PVP capped Pt nanoparticles do not show any
electrocatalytic activity toward oxygen reduction or methanol oxidation because of too strong
affinity of PVP to Pt.

Polyethylenimine (PEI) is a hydrophilic polymer with primary, secondary and tertiary

amino groups and overall positive charge in neutral aqueous solution. Because of abundant
positive charge, it is a widely used stabilizer to coat nanoparticles to achieve surface
functionalization. The positively charged amine groups stabilized the nanoparticles in
solution and can also be used to form self-assembled mono layers on common electrodes.

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 S. Laschi and coworkers developed glassy carbon electrodes modified with a
dispersion of multi-wall carbon nano tubes in PEI. It exhibits excellent electro catalytic
activity towards the analyte. PEI contains one of the highest densities of amine groups among
all polymers, this is the reason for the highly efficient dispersion of nanoparticles in PEI as
well as for the high electro activity of the PEI/CNT immobilized on the electrode surface.
Polyelectrolyte-capped Pt nanoparticles can be synthesized in aqueous solution, and their
assembly on electrodes can allow control of size distribution, shape, and surface density.
Thus, assembling charged Pt nanoparticles on an electrode may increase efficiency and
utilization.

Pan and co-workers demonstrated that self-assembled Pt nanoparticles electrode and

membrane-electrode assembly of polymer electrolyte fuel cells can be prepared by using
charged Pt nanoparticles with an ultra low Pt loading. Zaki and coworkers showed that nano
structured Pt electrodes were assembled from solution-prepared polyacrylate-capped Pt
nanoparticles by virtue of electrostatic and hydrophobic interactions with a cationic
polyelectrolyte poly(diallyldimethylammonium) (PDDA). Electrochemical characterization
of polyelectrolyte-stabilized Pt nanoparticles showed that these surfaces are catalytically
active for many reactions such as oxygen reduction, methanol oxidation, and hydrogen
oxidation.

Protein microtubule mediated synthesis of nanomaterials

The synthesis of increasingly miniaturized structures using alternative techniques is
strongly motivated by future applications in areas such as nanoelectronics. Microtubules,
highly oriented protein assemblies with defined surface functionalities, can serve as
bioorganic templates for the bottom-up synthesis of metal nanostructures (Figure 9).

Figure 9 Protein microtubule mediated synthesis of silver nanostructures

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 Depending on the kind of reducing agent and the pH value used, small silver particles
could be nucleated and densely bound to the tubular structure of the bio-template. These
particles could be enlarged to grain sizes of 10-30 nm by applying hydroquinone and silver
ions. g/protein structures with different morphologies are produced, from microtubules
densely covered with small Ag nanoparticles to continuous Ag nanowires. Even completely
continuous nanowires could be achieved by using a similar method.
The first step in the synthesis involves microtubule protein purification from porcine
brain by an in vitro assembly-disassembly process. The final protein concentration was about
1 mg mL-1. The microtubules were assembled in vitro in a buffer solution of 20 mM PIPES
(pH 6.8), 80 mM NaNO3, 0.5 mM Mg(NO3)2, and 1 mM EGTA by adding 0.25 M GTP and,
after 20 min, 10 mM taxol (from Taxus brevifolia) and warming the sample to 37 °C. The
microtubule formation was followed by turbidity measurements at λ = 360 nm and controlled
by electron microscopy. The assembled microtubules were chemically fixed in 0.1% glutaric
dialdehyde. The samples were finally dialyzed against PIPES buffer (diluted 10-fold with
H2O) to eliminate excess glutaric dialdehyde.
Synthesis of Silver Nanoparticles with NaBH4 involves addition of a 600- µL portion
of an aqueous AgNO3 solution (1 mM) to 60 µL of microtubule suspension and reduced by
rapidly adding 180 µL of an aqueous NaBH4 solution (2.5 mM) at 0 °C. The resulting
microtubule-bound silver nanoparticles was further developed with 240 µL of hydroquinone
solution (0.05 M in water) and 360 µL of AgNO3 solution (5 mM in water).
Similarly, synthesis of silver nanowires involves addition of a 60-µL sample of
assembled microtubules (fixed with glutaric dialdehyde, see above) to 630 µL with PIPES
buffer. The protein assemblies were then incubated with 30 µL of an aqueous AgNO3
solution (0.1 M) for 2 h at room temperature in the dark. In a second step, 240 µL of a
reduction bath containing hydroquinone (0.05 M in water) was added. The reaction was
typically stopped by adding an excess of Na2S2O3 (120 µL of a 0.25 M solution in water)
after 1, 2.5, or 7 min or by adsorption of the sample on a TEM grid. When the diluted
microtubules were incubated with only 10 µL of the aqueous AgNO3 solution, large silver
aggregates were attached to the microtubules, and no continuous silver coating was observed.
One problem, however, concerned the stability of these structures in solution, as they
tend to agglomerate into extended networks. There remains a great potential to apply these
metallization techniques to other protein assemblies to produce silver/protein composites with
interesting material properties. Highly ordered protein assemblies of tubular structure and
high geometric aspect ratio are used as bioorganic templates.

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Synthesis of nanoparticles using micro oraganism

The study of biosynthesis of nanomaterials offers a valuable contribution into

materials chemistry. The ability of some microorganisms such as bacteria and fungi to control
the synthesis of metallic nanoparticles should be employed in the search for new materials.
Biosynthetic methods have been investigated as an alternative to chemical and physical ones.
These methods can be divided into two categories depending on the place where the
nanoparticles or nanostructures are created as many microorganisms can provide inorganic
materials either intra- or extra-cellularly. For example, bacteria Pseudomonas strutzeri
isolated from silver mine materials is able to reduce Ag+ ions and accumulates silver
nanoparticles, the size of such nanoparticles being in the range 16–40 nm, with the average
diameter of 27 nm. The examples also include magnetotactic bacteria which produce
magnetite (Fe3O4) or greigite (Fe3S4) and diatoms which produce siliceous material. The
intracellular methods need a special ion transportation system into the microbial cell.
Formation of magnetite particles proceeds through a sequence of events: reduction of Fe(III)
to Fe(II), precipitation of amorphous oxide and subsequent transformation to magnetite.
Gold nanoparticles have also been synthesized in human cells, both in cancer and
non-cancer ones; the scanning microscopic images confirmed that their morphologies
differed significantly. This behaviour can have an implication to cancer diagnostics. In
contrast, extracellular synthesis of nanoparticles occurs in alkalothermophilic actinomycete,
Thermomonospora sp., which reduces gold ions. The metabolic activity of microorganisms
can lead to precipitation of nanoparticles in external environment of a cell, the fungi being
extremely good candidates for such processes. The extracellular synthesis of silver and gold
nanoparticles by the fungus Colletotrichumsp. or Aspergillusfumigatus has been reported. A
novel biological method for synthesis of silver nanoparticles using Vericillum was proposed
by Mukherjee et. al; a two-step mechanism was suggested. The first step involves trapping of
Ag+ ions at the surface of the fungal cells. In the second step, enzymes present in the cell
reduce silver ions. The extracellular production of metal nanoparticles by several strains of
the fungus Fusariumoxysporumhas been described by Duran et al. The presence of
hydrogenasein the F. oxysporiumbroth was demonstrated. This extracellular enzyme shows
excellent redox properties and it can act as an electron shuttle in metal reduction.
It was evident that electron shuttles or other reducing agents (e.g., hydroquinones)
released by microorganisms are capable of reducing ions to nanoparticles.The neem
(Azadirachtaindica) leaf broth and aqueous solution of silver nitrateorchloroauric acid were

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used for the extracellular synthesis of pure metallic silver and gold particles. The time
required for Ag+ and Au3+ ions to reduce was 4 h and 2 h, respectively, being extremely short
compared to both bacteria and fungi (24 h and 120 h). Surface active constituents of the leaf
broth stabilize nanoparticle suspensions – an aqueous suspension showed stability even after
4 weeks. Our aim in the present contribution was to synthesize and characterize silver
nanoparticles obtained by use of Penicillium fungi isolated from the soil.

Sonochemical synthesis

There are two types of effects mediated by ultrasound: chemical and physical. When
the quantity of bubbles is low - using standard laboratory equipment - it is mainly physical
rate acceleration that plays a role. For example, a specific effect is the asymmetric collapse
near a solid surface, which forms microjets (Figure 10). This effect is the reason why
ultrasound is very effective in cleaning, and is also responsible for rate acceleration in
multiphasic reactions, since surface cleaning and erosion lead to improved mass transport.

Figure 10 Microjets formed in a sonochemical method

For example, when ultrasound is applied to an Ullmann reaction that normally
requires a 10-fold excess of copper and 48 h of reaction time, this can be reduced to a 4-fold
excess of copper and a reaction time of 10 h. The particle size of the copper shrinks from 87
to 25 μm, but the increase in the surface area cannot fully explain the increase in reactivity. It
was suggested that sonication also assists in the breakdown of intermediates and desorption
of the products from the surface (Scheme 1).

Scheme 1 Ullmann reaction under sonochemical condition

Typically, ionic reactions are accelerated by physical effects - better mass transport -
which is also called "False Sonochemistry". If the extreme conditions within the bubble lead

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to totally new reaction pathways, for example via radicals generated in the vapor phase that
would only have a transient existence in the bulk liquid, we speak about "sonochemical
switching". Such a switch has been observed for example in the following Kornblum-Russel
reaction (Scheme 2) where sonication favors an SET pathway:

Scheme 2 Kornblum-Russel reaction under sonochemical condition

Applications for sonochemistry can be found in many areas, but sonochemical
processes are most widely developed for heterogeneous reactions. Currently, sonochemistry
is a multidisciplinary field in which chemists, physicists, chemical engineers and
mathematicians must cooperate to develop a better understanding of the processes that take
place within the collapsing bubbles to develop totally new applications. However, the
potential for making improvements in many types of reaction suggests that every chemical
laboratory should be equipped with at least one cleaning bath for simple trials.

Hydrodynamic Cavitation

Cavitation is the process in which formation and collapse of micro bubbles. This
process can be carried out by using venturi meter, orifice meter or valve. According to the
Bernoulli’s principle, if liquid is flowing through the orifice plate than velocity is increased.
If we are providing throttling valve before the caviting device than the throttling is possible.
Due to throttling, the pressure at vena contract point becomes decreases and its decreases
below the entering pressure i.e. vapor pressure. Due to the above condition millions of
cavities are generated. After the vena contract the pressure recovery of liquid is started at the
downstream side. In the downstream side process of cavity collapse occurs. In this process
some amount of energy is lost so that permanent pressure drop occurs. The intensity of cavity
collapse depends upon the amount of pressure drop. The value of pressure drop depends on
the size of the caviting device as well as flow rate of the liquid. If these two parameters are
maintained than we are getting the desired result. During the collapse of bubble the
temperature is increases very rapidly.

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Inorganic Nanomaterials

Inorganic nanoparticles are extremely important in modern technologies. They can be

synthesized easily and cheaply and can also be more readily integrated into devices. They
find application in variety of fields such as magnetic storage media, as metal oxide
nanoparticles to improve performance of oxide thin films as conducting media in commercial
gas and vapor sensors, as semiconductors for light-emitting devices and other areas related to
the energy sector, such as solar energy and energy storage devices (fuel cells, rechargeable
batteries, etc.), expanding the role of nanosized particles in the field of catalysis, art
conservation, and biomedicine.

Titanium Dioxide (TiO2)

Titanium dioxide (TiO2) has attracted great attention in the field of environmental
purification and can be used as a kind of solar energy cell. When irradiated with UV light,
TiO2 nano sized powder shows strong oxidizability and reducibility. It is well known fact that
TiO2 has three crystalline forms of anatase, rutile and brookite. Among these three crystalline
forms, rutile phase is the most thermodynamically stable, whereas brookite and anatase are
meta stable and transformed to rutile on heating. Different synthetic methods such as sol-gel
micro emulsion or reverse micelles, and hydrothermal synthesis have been used to derive the
nanoparticles of titanium dioxide. Compared to other methods, sol-gel process is regarded as
a good method to synthesis ultra-fine metallic oxide and has been widely employed for
preparing titanium dioxide nanoparticles.

Crystal Structure of TiO2 Nanoparticles

The unit cell structures of the rutile and anatase TiO2 (Figure 11). These two
structures can be described in terms of chains of TiO6 octahedra, where each Ti4+ ion is
surrounded by an octahedron of six O2- ions. The two crystal structures differ in the distortion
of each octahedron and by the assembly pattern of the octahedra chains. In rutile, the
octahedron shows a slight orthorhombic distortion; in anatase, the octahedron is significantly
distorted so that its symmetry is lower than orthorhombic. The Ti-Ti distances in anatase are
larger, whereas the Ti-O distances are shorter than those in rutile. In the rutile structure, each
octahedron is in contact with 10 neighbor octahedrons (two sharing edge oxygen pairs and
eight sharing corner oxygen atoms), while, in the anatase structure, each octahedron is in
contact with eight neighbors (four sharing an edge and four sharing a corner). These

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differences in lattice structures cause different mass densities and electronic band structures
between the two forms of TiO2.

Figure 11 Crystal Structure Of TiO2 Nanoparticals

Synthesis of TIO2 by Sol-gel method

The sol-gel method is a versatile process used in making various ceramic materials. In
a typical sol-gel process, a colloidal suspension, or a sol, is formed from the hydrolysis and
polymerization reactions of the precursors, which are usually inorganic metal salts or metal
organic compounds such as metal alkoxides. Complete polymerization and loss of solvent
leads to the transition from the liquid sol into a solid gel phase. Thin films can be produced
on a piece of substrate by spin-coating or dip-coating. A wet gel will form when the sol is
cast into a mold, and the wet gel is converted into a dense ceramic with further drying and
heat treatment. A highly porous and extremely low-density material called an aerogel is
obtained if the solvent in a wet gel is removed under a supercritical condition. Ceramic fibers
can be drawn from the sol when the viscosity of a sol is adjusted into a proper viscosity
range. Ultrafine and uniform ceramic powders are formed by precipitation, spray pyrolysis,
or emulsion techniques. Under proper conditions, nanomaterials can be obtained.

A 20 ml of solution Titanium tetra iso propoxide was added drop by drop into the 22
ml of solution containing 10 ml of iso-propanol and 12 ml deionised water under constant
stirring at 80º C into the round bottom beaker. After 1 h, concentrated HNO3 (8 ml) mixed
with deionised water was added into the TTIP solution and keep it under constant stirring at
60 ºC for 6 h highly viscous sol gel was obtained. The prepared sol-gel was heated at 300 ºC
for 2 h in the open atmosphere. After annealing, the TiO2 nano crystalline 2 g powder was
obtained. Further preparation of TiO2 film, the prepared powder was added in the ratio of

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1:10 of the solution of iso-propanol. The TiO2 nanoparticles deposited on titanium substrate
(0.5 cm2) using the dip coating method.

Applications of TiO2

In is used in the paper industry for improving the opacity of paper as a catalyst in
synthesis of biscoumarins (Scheme 3).

Scheme 3 Nano TiO2 catalysed synthesis of biscoumarins

Titanium oxide exhibits good photo catalytic properties, hence finds application in
antiseptic and antibacterial compositions, degrading organic contaminants and germs, UV-
resistant material, manufacture of printing ink, self-cleaning ceramics and glass, coating, etc.,
making of cosmetic products such as sunscreen creams, whitening creams, morning and night
creams, skin milks, etc.

Zinc oxide (ZnO)

Nanostructured ZnO materials have received broad attention due to their distinguished
performance in electronics, optics and photonics. From the 1960s, synthesis of ZnO thin films
has been an active field because of their applications as sensors, transducers and catalysts.
ZnO is a key technological material. The lack of a centre of symmetry in wurtzite, combined
with large electromechanical coupling results in strong piezoelectric and pyroelectric
properties and the consequent use of ZnO in mechanical actuators and piezoelectric sensors.
In addition, ZnO is a wide band-gap (3.37 eV) compound semiconductor that is suitable for
short wavelength optoelectronic applications. The high exciton binding energy (60 meV) in
ZnO crystal can ensure efficient excitonic emission at room temperature and room
temperature ultraviolet (UV) luminescence has been reported in disordered nanoparticles and
thin films. ZnO is transparent to visible light and can be made highly conductive by doping.
ZnO is a versatile functional material that has a diverse group of growth morphologies, such
as nanocombs, nanorings, nanohelixes/nanosprings,nanobelts, nanowires and nanocages.

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Crystal and surface structure of ZnO

Wurtzite zinc oxide has a hexagonal structure (space group C6mc) with lattice
parameters a = 0.3296 and c = 0.52065 nm. The structure of ZnO can be simply described as
a number of alternating planes composed of tetrahedrally coordinated O2− and Zn2+ ions,
stacked alternately along the c-axis (Figure 12).

Figure 12 The wurtzite structure model of ZnO. The tetrahedral coordination of Zn–O
The tetrahedral coordination in ZnO results in noncentral symmetric structure and
consequently piezoelectricity and pyroelectricity. Another important characteristic of ZnO is
polar surfaces. The most common polar surface is the basal plane. The oppositely charged
ions produce positively charged Zn-(0001) and negatively charged O-(000ˉ 1) surfaces,
resulting in a normal dipole moment and spontaneous polarization along the c-axis as well as
a divergence in surface energy. To maintain a stable structure, the polar surfaces generally
have facets or exhibit massive surface reconstructions, but ZnO- ±(0001) are exceptions they
are atomically flat, stable and without reconstruction. Efforts to understand the superior
stability of the ZnO ±(0001) polar surfaces are at the forefront of research in today’s surface
physics. The other two most commonly observed facets for ZnO are {2ˉ1 ˉ10} and {01ˉ10},
which are non-polar surfaces and have lower energy than the {0001} facets.

Zinc oxide finds application is various areas. It is used in the manufacture of rubber
and cigarettes (used as a filter). Popularly known calamine lotion is made out of zinc oxide
powder. It is also used in a host of other creams and ointments that are used to treat skin
diseases. Ceramic industry has a number of uses for zinc oxide powder. It is also used as an
additive in food products such as breakfast cereals. Various paints use zinc oxide as a coating
agent and as an additive in the manufacture of concrete.

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Nano cadmium oxide (CdO)

Cadmium oxide has gained tremendous attention due to its interesting properties like
direct band gap of 2.3 eV. It is widely used in the applications like the preparation of
cadmium coated baths and manufacture of paint pigments. Nanostructure CdO was
synthesized by sol – gel method using metal precursor cadmium acetate. Cadmium acetate
was added slowly in 500 ml clear solution of starch and distilled water and the solution was
stirred. While stirring, equimolar ammonia in aqueous solution was added drop by drop. Then
stirring was carried for another two hours and the solution was kept overnight. Next day the
solution was filtered and precipitate of CdO was obtained which was heated overnight at
80ºC. Next day crystalline form of CdO was sintered up to 600ºC. At 80ºC the colour of CdO
was light red and at 600ºC, it was reddish brown.

Polyaniline-CdO nanocomposite was obtained by in-situ polymerization. Initially

polymerization of monomer aniline was initiated by drop wise addition of ammonium
peroxidisulphate in acidic medium in which specific quantity of synthesized CdO powder
was added. The stirring was continued for 2 hours and then solution was kept overnight. Next
day, the mixture was filtered, washed with distilled water and the methanol and then dried at
80ºC for overnight. By changing the weight percentage of CdO with aniline monomer (5%,
10%, 20%) a series of Polyaniline-CdO nano composites was obtained.

Applications of CdO

Cadmium oxide was used in applications such as photodiodes, photovoltaic cells,

solar cells, transparent electrodes, liquid crystal displays, IR detectors, gas sensors and
antireflection coat. Major uses for cadmium oxide are as an ingredient for electroplating
baths, and in pigments.

Nano Cadmium sulphide (CdS)

Cadmium sulfide is yellow in color and is a semiconductor of electricity. It exists

as two different polymorphs, hexagonal greenockite and cubic hawleyite. CdS in bulk has
band gap energy of 2.42eV at 300K with absorption maxima at 515 nm. It can attain three
types of crystal structures namely wurtzite, zinc blend and high pressure rock-salt phase
(Figure 13). Among these, wurtzite is the most stable of the three phases and can be easily
synthesized. Wurtzite phase have been observed in both the bulk and nanocrystalline CdS
while cubic and rock-salt phases are observed only in nanocrystalline CdS.

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 Figure 13 Structure of CdS

The wurtzite form comprises of hexagonal close packing (hcp) in which the stacking
sequence of the atoms is ABABAB…, while, the zinc blende and rock salt structure have the
stacking sequence of the atoms as ABCABCA…, i.e., called cubic close packing (ccp)
(Figure 14) In hexagonal wurtzite and cubic zinc blend, each atom is coordinated to four
other atoms in tetrahedral fashion such that each atom has four neighboring atoms of the
opposite type, whereas in rock-salt each atom is coordinated to six other atoms in octahedral
fashion such that each atom has six neighboring atoms of the opposite kind.

Figure14 Representative diagram for the unit cell for crystal structure of CdS, showing (a)
wurtzite (hcp), (b) zinc blend (ccp) and (c) rock salt (ccp) phases.
The CdS nanoparticles were synthesized by chemical precipitation method using
Cadmium acetate and sodium sulfide as the starting materials. 0.1 M solution of
Cd(CH3COO)2 and Na2S reactants was prepared using millipore water. 50 ml of 0.1M
cadmium acetate solution was taken in 250 ml Round bottom flask and stirred for 30 minutes

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using magnetic stirrer. After 20 mins. 0.01M tetrabutylammonium bromide (TBAB)
dissolved in water was added to it and continued stirring for 30 mins to get homogeneous
solution and then 0.1M solution of sodium sulfide was added dropwise to the solution of
cadmium acetate under continuous stirring until the formation of yellow precipitate and
stirring was continued for 2h to complete the reaction. The pH was maintained at 9-10 by
adding ammonia solution in basic medium. The chemical reaction is,

The solution was allowed to settle down for 2h, and the particles were precipitated
into ethanol. The solid yellow product was washed by suspending them in ethanol. The
reaction product was repeatedly washed with ethanol to clear the surfactant impurities from
the CdS nanoparticles and centrifuged for 20 mins for three times with ethanol at high rpm
level. And then the product was dried at 150 ºC for 3h under reduced pressure at ambient
temperature.
Synthetic cadmium pigments based on cadmium sulfide are valued for their good
thermal stability, light and weather fastness, chemical resistance and high opacity. As a
pigment, CdS is known as cadmium yellow. Cadmium sulfide is also used in the production
of solar cells where it is used as a buffer layer in the manufacture of CIGS (Copper -Indium-
Gallium-Selenide) solar cells.

Reaction in Nanospace
A wide array of self-assembled molecular capsules based on various building blocks
and noncovalent interactions has been developed in the last decade. The nanospace within
these supramolecular capsules is generally in the range of 300– 500 A˚ which is sufficient for
the selective encapsulation of one large or a number of smaller molecules. The structure of
the different capsules varies significantly, and as a result guest shielding and guest exchange
rates strongly depend on the capsule applied. A diversity of chemical processes has been
carried out within molecular capsules and the effects observed so far are, although academic,
very interesting. Reactions can be accelerated and the selectivity of a chemical process can be
changed completely. These observations can be explained by stabilization of the reaction
transition state by the capsule (based on enthalpic and entropic contributions) or by
concentration effects in the case of bimolecular reactions, such as Diels–Alder reactions.
More important are the unique reaction selectivities induced by the novel finite
microenvironment within the capsule. The size and shape of the nanoreactor’s cavity and that
of the nanoreactor’s gates can control the substrate selectivity by controlling the access to the

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cavity. In a same manner it can protect an active-site located in the cavity that otherwise
would be poisoned by chemicals present in solution.

The regio and chemo selectivities can be changed by the capsule by changing the ratio
of reaction rates of competing pathways. This was for example observed for encapsulated
rhodium complexes that were used as hydroformylation catalysts. In addition to these effects,
reaction intermediates have been observed in nanoreactors that otherwise have too short
lifetimes for identification. In these occasions the reaction rate of the subsequent step after
the formation of the intermediate is slowed down by the nanocapsule. Product inhibition,
which is a frequently encountered problem in bimolecular coupling reactions carried out
within enclosed cavities, is fundamentally related to the former. The coupling product might
have a higher affinity for the capsule than the substrates, and consequently product release
from the nanoreactor becomes the slowest step in the reaction. Product inhibition can prohibit
the utility of nanoreactors as true catalysts.

Self-assembled capsules also have guest exchange mechanisms via partial

disassembly of the capsule, whereas exchange for the covalent analogues is restricted to
portal slippage. It is this unique property that enables the combination of complete
encapsulation with sufficiently fast in–out exchange, which might prove to be the advantage
in the catalysis application. Although the research field is still in its infancy, several examples
of reactions carried out within self-assembled nanoreactors appeared and demonstrate the
power of the concept. Detailed studies are still needed to fully understand the mechanisms
behind the effects observed when carrying out reactions in nanoreactors. However, molecular
capsules have also been used to control reactions that take place outside the capsule for
example by controlling the release of reagents, making the nanoreactor applications virtually
unlimited.

Nanoconfinement

Nanoconfinement is receiving increasing interest in the field of energy storage and

has been applied to different metal hydride systems in order to improve their properties for
hydrogen storage. Modified hydrogen sorption kinetics and thermodynamics of metal
hydrides have been achieved by nano size effects. Recent advancements in nanoscience and
nanotechnology, increasing numbers of chemical reactions are conducted in confined or
nearly confined nanospaces. Thus, reactions between a few organic molecules and between
bio-molecules, or the fabrication of inorganic and metallic nanoclusters is confined to a

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nanospace, exhibit distinct properties compared to the same processes involving macroscopic
systems. Beyond these cases, the stabilization of labile intermediates by an open-ended self-
folding cavitand, of reaction products in mesoporous silica and of nucleotide dimers
(duplexes) formed via hydrogen-bonding inside self-assembled coordination cages
(potentially pertinent to molecular information processing in DNA-based computing) was
recently observed. Finally, this effect is expected to be important in the growing
nanotechnological utilization of chemical reactions conducted within confined nanospaces, as
well as in theoretical physical chemistry in general, due to the fundamental deviations from
classical thermodynamics of macroscopic systems.

Nanocapsules

A nanocapsule is a nanoscale shell made from a nontoxic polymer. They are vesicular
systems made of a polymeric membrane which encapsulates an inner liquid core at the
nanoscale. Nanocapsules have many uses, including promising medical applications for drug
delivery, food enhancement, nutraceuticals, and for self-healing materials. The benefits of
encapsulation methods are for protection of these substances against adverse environment, for
controlled release, and for precision targeting. Nanocapsules can potentially be used as MRI-
guided nanorobots or nanobots, although challenges remain.

The nano-sized structure of nanocapsules allows permeating through cell membranes,

which makes them effective carriers of medicine in biological systems. The specific
processing of nanocapsules gives them unique properties in how they release drugs in certain
situations. Generally, there are three physico-chemical release mechanisms that are used to
release the drug or medicine from the polymeric shell of the nanocapsule.

The delivery of nanocapsules could happen through different mechanism on such

process is hydration and diffusion. In this release mechanism the nanocapsule will swell due
to the effects of hydration. Once the nanocapsule is has swollen to a point where it stretches,
the polymeric membrane it will allow for diffusion of the drug through the polymeric
membrane and into the biological system.

Another type of mechanism for the delivery of nanocapsules is enzymatic reaction.

The polymer shell must be first selected to coordinate with the enzymes produced by the
human body to produce and enzymatic reaction. This reaction will cause a rupture in the
polymeric membrane which allows the drug to be dispersed into the system. After the rupture
the drug dissociates from the swelled nanocapsule and diffuses out into the rest of the cell.
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Cavitands

Inspired by the exquisite specificity of biomolecules such as antibodies for target

antigens, attempts were made through supra molecular chemistry approach to do the same for
small molecule targets through the use of synthetic receptors called cavitands. These
molecules have the potential to be selective, because of their unique biomimetic
nanostructures. Cavitands derive their name from the shape of their cavities (Figure 15).
These molecules are designed to bind target molecules to form guest-host complexes. By
tuning the cavity depth, shape, and chemical functionality that controls the synergistic
interactions with analyte molecules, cavitands for a range of molecular targets may be
designed and synthesized. This strategy for selectivity-enhancement is fundamentally
different from that used in other chemically selective coatings (for example, polymers) that
rely on the solubility of the targets with the coating layer.

Figure 15 Three cavitands: (a) MeCav (methylene-bridged), (b) PzCav (pyrazine-bridged),

and (c) QxCav (quinoxalines-bridged) with varying depths and therefore complexing ability
with target molecule.
Although target molecules may bind selectively to such tailored cavitand molecules, it
is equally important to transduce the binding event by using an appropriate technique that has
high sensitivity. A real-time, label-free, optical technique called surface plasmon resonance
(SPR), refractive index changes induced by analyte-cavitand interactions provide selective
signals for sensitive chemical vapor detection.
Three cavitands named MeCav (for methylene-bridged), PzCav (pyrazine-bridged),
and QxCav (quinoxalines-bridged) shows selectivity toward aromatic vapors (Figure 15). The
presence of alkyl tails (R) at the bottom of the cavity is to make them soluble in common
solvents such as chloroform. Cavitand solutions (0.38 mM) in chloroform were spin coated
onto surface plasmon resonance substrates (50-nm thick gold-coated cover glass). Spin

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coating was performed at 4000 rpm for 60 s at room temperature. The spin coating
parameters gave a film thickness (confirmed using spectroscopic ellipsometry) of nearly 4
nm. For targets, a variety of analyte vapors belonging to different chemical classes were
studied. QxCav with the deepest cavity was designed to form guest-host complexes with
aromatic vapors, whereas cavitands with shallower cavities (such as MeCav and PzCav) were
not expected to be as selective toward such guest molecules. Cavitands finds application as a
platform for the study of protein structure and detect sarcosine in water and urine solutions.

Cucurbiturils
Cucurbiturils are macrocyclic molecules consisting of glycoluril repeat units. These
compounds are particularly interesting to chemists because they are molecular containers that
are capable of binding other molecules within their cavity (Figure 16).

Figure 16 Structure of various cucurbiturils

The name is actually derived from the resemblance of this molecule with a pumpkin
of the family of Cucurbitaceae. The cavity of cucurbit[6]uril has nanoscale dimensions with
an approximate height of 9.1 Å, outer diameter 5.8 Å and inner diameter 3.9 Å. Cucurbiturils
are commonly written as cucurbit[n]uril, where n is the number of glycoluril units. Two
common abbreviations are CB[n], or simply CBn.

Figure 17 Synthesis of CBn homologues by condensation of glycoluril (1) and formaldehyde

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 The synthesis of cucurbiturils was first reported in 1905 by Behrend. Cucurbiturils
can be synthesisd by the acid-catalyzed condensation of glycoluril and formaldehyde (Figure
17).
Cucurbiturils are efficient host molecules in molecular recognition and have a
particularly high affinity for positively charged or cationic compounds. High association
constants with positively charged molecules are attributed to the carbonyl groups that line
each end of the cavity and can interact with cations is a similar fashion to crown ethers. The
affinity of cucurbiturils can be very high.
Host guest interactions also significantly influence solubility behavior of
cucurbiturils. Cucurbit[6]uril dissolves poorly in just about any solvent but solubility is
greatly improved in a solution of potassium hydroxide or in an acidic solution. The cavitand
forms a positively charged inclusion compound with a potassium ion or a hydronium ion
respectively which have much greater solubility that the uncomplexed neutral molecule.
Cucurbiturils host-guest properties have been explored for drug delivery vehicles. The
potential of this application has been explored with cucurbit[7]uril that forms an inclusion
compound with the important cancer fighting drug oxaliplatin. Encapsulation of fluorescent
in Cucurbiturils can leads to numerous applications. Benefits of encapsulation are
solubilazation, deaggregation, photostabilization. Cucurbiturils forms stable complexes with
various guests, including drug molecules, amino acids and peptides, saccharides, dyes,
hydrocarbons, perfluorinated hydrocarbons, and even high molecular weight guests such as
proteins (e.g., human insulin).

Zeolites

Zeolites are hydrated aluminosilicate minerals made from interlinked tetrahedra of

alumina (AlO4) and silica (SiO4). In simpler words, they're solids with a relatively open,
three-dimensional crystal structure built from the elements aluminum, oxygen, and silicon,
with alkali or alkaline-earth metals (such as sodium, potassium, and magnesium)
plus water molecules trapped in the gaps between them (Figure 18). Zeolites form with many
different crystalline structures, which have large open pores (sometimes referred to as
cavities) in a very regular arrangement and roughly the same size as small molecules. There
are about 40 naturally occurring zeolites, forming in both volcanic and sedimentary rocks;
according to the US Geological Survey, the most commonly mined forms include chabazite,
clinoptilolite, and mordenite.

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 Figure 18 Basic zeolite structure (left),crystal structure of Zeolite (right)

Dozens more artificial, synthetic zeolites (around 150) have been designed for
specific purposes, the best known of which are zeolite A (commonly used as a laundry
detergent), zeolites X and Y (two different types of faujasites, used for catalytic cracking),
and the petroleum catalyst ZSM-5 (a branded name for pentasil-zeolite). Although all zeolites
are aluminosilicates, some contain more alumina, while others contain more silica. Alumina-
rich zeolites are attracted to polar molecules such as water, while silica-rich zeolites work
better with nonpolar molecules.

Properties: Zeolites are very stable solids that resist the kinds of environmental
conditions that challenge many other materials. High temperatures don't bother them because
they have relatively high melting points (over 1000°C), and they don't burn. They also resist
high pressures, don't disssolve in water or other inorganic solvents, and don't oxidize in the
air. The counter-cations in zeolites are mobile, and may easily be exchanged. This results in
ion exchange capability utilized e.g. in detergents and in waste water purification.

One of the major uses of zeolites is as heterogeneous catalysts. The cage-like structure
of zeolites makes them useful in all sorts of ways. One of the biggest everyday uses for
zeolites is in water softeners and water filters. In ion-exchange water softeners, for example,
hard water (rich in calcium and magnesium ions) is piped through a column filled with
sodium-containing zeolites. The zeolites trap the calcium and magnesium ions and release
sodium ions in their place, so the water becomes softer but richer in sodium. Many everyday
laundry and dishwasher detergents contain zeolites to remove calcium and magnesium and
soften water so they work more effectively.

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 Two other very common, everyday uses of zeolites are in odor control and pet litter;
in both, the porous crystalline structure of the zeolites helps by trapping unwanted liquids and
odor molecules. This simple idea, so effective in our homes, has much more important uses
outside them: zeolites have proved extremely effective at removing radioactive particles
from nuclear waste and cleaning up soils contaminated with toxic heavy metals. (Following
the Fukushima nuclear disaster in Japan in 2011, rice farmers spread zeolites on their fields in
an attempt to trap any lingering radioactive contaminants.) The many other uses for zeolites
includes concrete production, soil-conditioners, and animal food.

An important use for zeolites is as catalysts in drug (pharmaceutical) production and

in the petrochemical industry, where they're used in catalytic crackers to break large
hydrocarbon molecules into gasoline, diesel, kerosene, waxes and all kinds of other
byproducts of petroleum. Again, it's the porous structure of zeolites that proves important.
The many pores in a zeolite's open structure are like millions of tiny test tubes where atoms
and molecules become trapped and chemical reactions readily take place. Since the pores in a
particular zeolite are of a fixed size and shape, zeolite catalysts can work selectively on
certain molecules, which is why they're sometimes referred to as shape-selective
catalysts (they can select the molecules they work on in other ways beside shape and size,
however). Like all catalysts, zeolites are reusable over and over again.

Metal-organic framework

Metal–Organic Frameworks (MOFs) or porous coordination networks are a class of

advanced materials designed by employing various metal ions and organic linkers. MOFs
have emerged as an extensive class of crystalline materials with high porosity in nature.
Unlike other porous materials like zeolites, activated carbon, and metal-complex hydrides
etc., MOFs are branch of materials having many virtues such as thermal stability, discrete
ordered structure, ultra-low densities (i.e. 1.00 to 0.09 g cm-3), large internal surface area
extending beyond 6000 m2/g, ease of synthesis and with broad-spectrum of properties suited
for physical and chemical applications. These striking features led to incessant research for
the development of many new porous materials. On an elemental level, MOFs epitomize the
elegance of chemical structures and the relevance of combination of inorganic and organic
components.

In contrast to the nomenclature, MOF materials can be developed by connecting

together both metal ions or metal oxides and polytopic organic struts or linkers. Organic

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linkers with different functionality, i.e. bidentate to polydentate aromatic carboxylates
(Figure 19) have been used to develop the new MOFs.

Figure 19 Potential polytopic organic acids as linkers in MOFs. (i) oxalic acid, (ii)
terephthalic acid, (iii) trimesic acid, (iv) adamantane-1,3,5,7-tetracarboxylic acid, (v) fumaric
acid, (vi) 4,5-imidazoledicarboxylic acid, (vii) 1,4-butanedicarboxylic acid, (viii) 4,6-
dihydroxy benzene-1,2,5-trisulfonic acid, (ix) biphenyl-4,40 -dicarboxylic acid, (x) 2,5-
dihydroxyterephthalic acid, (xi) 6,60 -dichloro-4,40 -di(pyridin-4-yl)-1,10 -binaphthyl-2,20 -
diol, (xii) 2,6-naphthalenedicarboxylicacid and (xiii) 1,3,5-benzenetribenzoic acid.
Novel Metal–Organic Framework materials can be achieved, when several
influencing factors are taken into consideration. While preserving the structural frame work
building units is the most important, significant attention has been paid to the synthesis of
new organic ligands for linkers and optimal conditions for development of metal–organic
ligand bond. The characteristics of ligand such as length of ligand, bulkiness, bond angles,
chirality, etc., and the geometries attained by the metal ions expressively influence the
structure of MOFs.
In recent years, the advantages of hydrothermal technique in the crystal engineering
have been more explored. In the case of MOFs, hydrothermal synthesis is adorable due to
two reasons. Firstly, the solubility problem of heavy organic molecules under the
experimental conditions can be minimized. Secondly, nucleation process can be initiated
rapidly for the formation of rare complexes under the same experimental conditions. As the
viscosity of water is reduced under these conditions, the activity of mobilization of precursors
is favored. Under these conditions thermodynamically meta stable phases of coordination
networks or MOFs can be isolated. The crystal growth can be enhanced in steel autoclaves
placed in programmable hot air ovens at running temperatures below 300 C with certain
retention time. Different temperatures are maintained at the opposite ends of the vessel, hotter
end dissolves the nutrients whereas growth of seeds begins at cooler side of the vessel.

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 MOF can be employed for separation of small gases such as hydrogen, methane,
acetylene, oxygen, carbon dioxide, and nitrogen is very important for industrial processes
because these small gases can be utilized as energy sources and raw materials for the
production of a range of chemical product compounds. Similarly MOFs can be used for
CO2 capture, methane storage, C2H2 / C2H4 separation, synthesis of luminescent materials
and in heterogeneous catalysis.
Porous silicon
Porous silicon was discovered in 1956 by Uhlir while performing electropolishing
experiments on silicon wafers using an electrolyte containing hydrofluoric acid (HF). He
found that under the appropriate conditions of applied current and solution composition, the
silicon did not dissolve uniformly but instead fine holes were produced, which propagated
primarily in the direction in the wafer. Therefore, porous silicon formation was obtained by
electrochemical dissolution of silicon wafers in aqueous or ethanoic HF solutions.
Porous silicon is a very promising material due to its excellent mechanical and
thermal properties, its obvious compatibility with silicon-based microelectronics and its low
cost. Its large surface area within a small volume, its controllable pore sizes, its convenient
surface chemistry, and the ability to modulate its refractive index as a function of depth
makes porous silicon a suitable dielectric material for the formation of multilayers
In the 1990s Leigh Canham published his results on red-luminescence from porous
silicon, that was explained in terms of quantum confinement of carriers in nano-crystals of
silicon which are present in the pore walls. Since that time, the interest of researchers and
technologists to this material (and other porous semiconductors as well) is constantly growing
and the number of publications dedicated to this class of materials increases every year. With
the discovery of efficient visible light emission from porous silicon came an explosion of
work focused on creating silicon-based optoelectronic switches, displays, and lasers. During
the last twenty years, the optical properties of porous silicon have become a very intense area
of research.
All these features also leads, on one hand, to interesting optical properties by mixing
silicon with air in the effective medium approximation. On the other hand the pores allow the
penetration of chemical and biological substances, liquids, cells, molecules to change i.e. the
optical behavior of the original system. These effects inspired research into different
applications like optical sensing applications and biomedical applications.

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Electrochemical etching of porous silicon
One of the most important advantages of porous silicon is its simple and easy
preparation. Since the first studies of Uhlir and Turner, and lately Cahnam, porous silicon has
been mainly obtained by electrochemical dissolution of silicon wafers in solutions based on
hydrofluoric acid (HF). A schematic of the porous silicon formation process can be seen in
figure 20. The surface of a silicon wafer, contacted on the back, is in contact with a solution
containing hydrofluoric acid (HF). After applying a voltage (in the right direction) between
the wafer backside contact and an electrode in the HF solution, a pore growth by silicon
dissolution starts, provided certain key parameters are set correctly.

Figure 20 Schematic diagram of the porous silicon anodization circuit.

Anodization parameters
The porous silicon formation process with electrochemical anodization has been
widely developed by many authors. The parameters that influence on this formation process
are the substrate doping, the current density, the HF concentration: the higher the
concentration, the lower the pore size and the porosity. HF concentration determines the
upper limit to current density values. With a fixed and low HF concentration the range over
which the current density can be varied is short, and it becomes wider by increasing the HF
concentration. The solvent where the HF is diluted is an important factor. Since porous
silicon is organophilic and hydrophobic, the use of ethanol guarantees a higher homogeneity,
due to a better wettability of the surface than deionized water.
Etching time is an important factor. Longer etching times lead to thicker layers, but
for long times an anisotropy in depth in the layer due to the chemical action of the electrolyte
is introduced. The illumination during the etch is essential for n-type substrates. The porosity,
thickness, pore diameter and microstructure of porous silicon depend on the anodization
conditions.

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Porous silicon finds application in different areas a shown in the table given below
Application area Role of porous sillicon Key property
Optoelectronics LED, Waveguide, Field Efficient electroluminescence, Tunability of
emitter, Optical memory refractive index, Hot carrier emission
Non- linear properties
Micro-optics Fabry-perot Filters Refractive index modulation
Photonic bandgap Regular macropore array
structures, all optical Highly non-linear properties
switching
Energy Antireflection coatings Low refractive index
conversion Photo-electrochemical Photocorrosion cells
cells
Environmental Gas sensing Ambient sensitive properties
monitoring
Microelectronics Micro-capacitor High specific surface area
Insulator layer High resistance
Low-K material Electrical properties
Wafer Buffer layer in Variable lattice parameter
technology heteroepitaxy High etching selectivity
SOI wafers
Micromachining Thick sacrificial layer Highly controllable etching

Biotechnology Tissue bonding Tunable chemical reactivity

Biosensor Enzyme immobilization

Nanocatalysis

Catalysis is one of the longest-established uses for nanoparticles. Aluminium, iron,

titanium dioxide, clays, and silica have all been used as catalysts in nanoparticle form for
many years. The properties of these particles which make them useful as catalysts has not
been fully understood. Nanoparticle catalysts have a very large surface area, which has a
straightforward positive effect on reaction rate. However, there are structure- and shape-
based properties at the nanoscale, which can also effect the catalytic activity of a material.

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 Homogeneous nano catalysts (Figure 21) are used in the same medium as the
reactants for nanoparticles. This typically means a solution or suspension of nanoparticles in
a solvent. The most important issue to consider when designing a nanocatalyst for use in a
solution is to prevent aggregation, nanoparticles are naturally attracted towards one another in
these conditions, and will clump together to form larger particles if not prevented from doing
so, removing their large surface area and other benefits.

Figure 21 Nanoparticle catalysts can be much more active and selective than the same
materials in bulk or larger particle form - partly due to the increased surface area, but also due
to additional size effects.

The most effective way to stabilize nanoparticles in solution is to attach long chain
molecules to the surface. These make it impossible for the nanoparticles to get so close that
they stick together. However, they can also reduce the access to the nanoparticle surface for
the reacting molecules, decreasing overall catalytic activity. The other main concern with
homogeneous nanocatalysts is recovery. Nanoparticles are notoriously difficult to remove
from a solution, and the extra steps needed to do so could completely negate the process
simplification due to using the catalyst in the first place. If the nanoparticles cannot be
recovered, they pose an environmental risk, as well as threatening the profitability of the
process. Most nanoparticles cannot be destroyed by incineration, and the effects of
nanoparticle accumulation in ecosystems are largely unknown.

Heterogeneous Nanocatalysts

Heterogeneous catalysis is often considered to be more environmentally friendly. This

involves a catalyst which is in a different phase to the reactants. The catalyst is usually solid,

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or immobilized on a solid inert matrix (Figure 22). This gets around the issue of waste and
recoverability, as the solid catalyst can in most cases simply be filtered out.

Figure 22 Heterogeneous catalysts are much easier to remove from the reaction mixture, and
are also more adaptable to continuous flow processes

A great deal of research has been done to investigate the catalytic potential of various
nanoparticle-support systems. Recent examples include palladium, iron, gold, nickel and
platinum nanoparticles. Supports used range from silica or aluminum to carbon fibres.
Another area of heterogeneous nanocatalysts which has been explored is nanostructured
solids. Nanoporous materials can be manufactured by growing the solid material around a
molecular template. Nanoscale features can also be etched into the surface of a catalyst using
standard lithography techniques - this can allow a degree of control over reactant flow on the
catalyst surface, as well as increasing surface area.

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