13 Nanochemistry

There are more atoms in a single grain of sand than grains of sand on Earth.

CHAPTER OUTLINE
13.1 Introduction 13.4 Bottom-up and top-down Approaches in Nanc
13.2 Why Properties of Nanomaterials Differ from technology
Other Materials? 13.5 Nanoscale Materials
13.3 Nanochemistry and Applications 13.6 Future Prospects of Nanotechnology

13.1 INTRODUCTION
Nanochemistry is the study of the fundamental principles of molecules and structureswit
at least one dimension roughly between 1 and 100 nanometers. These structures are
no
nanostructures. Nanotechnology is the application ofthese nanostructures into useful nanoscale devi
The difference between nano science the
chemistry and nano
technology is that the former 1Sre s at
study of relationship between various phenomena, physical properties and material dimen
nano-scale, whereas the later is application of the nano-structures and principles relatea
make nano-scale dimensions and material.
scientists
During the last few years, a little word with a big potential has diverted the
all over the globe. That word is "nano". Chemists, attenuou
mpuler
biologist, doctors, physicists, engineers,
ding n
scientists are all intimately involved in
nano-development. Nanotechnology is the umdersta
control of matter al the nanoscale, at dimensions between ters

approximately I and 100 nano ie, on

Theprefix "nano" means one billionth. One nanometer is 1/1000, 000, 000 of a meter
n o m e t e r s

thousands millionth of a meter. To get a sense of the nano scale, a human hair measures
across, a bacterial cell measures a few hundred nanometers across, and the smallest
sin
80,000 that .
features
nallestithings
commonly etched on a commercial microchip are around 130
nanometers across. The Si
observable with the unaided human eye are 10,000 nanometers across. Just ten hydrogen atoms r e db l o o d

silicon atoms in a line make one nanometer. t s a

really very small indeed. For comparis is define
cell is approximately 7000 nm wide and a water molecule is almost 0.3 nm across
s s . Nanoscalee t h a tthe

to be from 100 nm down to the size of atoms (approvimatey 0.2

nm) because it is at this de
anerties of materials can be very difereni from those at a larger scale.
518
 NANOCHEMISTRY 519
13.2 WHY PROPERTIES OF NANOMATERIALS DIFFER FROM OTHER
MATERIALS
The physical, chemical and mechanical properties of nanomaterials are based upon the structure
Caanomaterials. This is because of the size of the particles being with in nanoscale (1-100 nm). The
wo main factors for the difference in properties are due to increased relative surface area and quantum
effects.
With decrease in size of the particles, a greater proportion of the particles are found at the surface
as compared two those in the bulk. As a result properties such as reactivity, strength and electrical etc.
are changed or enhanced. A given mass of material in nanoparticle form will be much more reactive
than the same mass of material made up of larger particles. It is because the growth processes and
catalyticchemical reactions which occur at surfaces.
The change in properties from macro-scale to nano scale can be observed by taking a simple
example of gold. If we start cutting gold from inches to centimeters from cm to mm and from mm to
micros, we will notice the change in properties.
But when these um size gold particles are further sliced into nano size particles, every thing will
be changed including gold's colour, melting point and chemical properties. Melting point of nano gold
is less than that of bulk gold melting point. Similarly instead of yellow colour, nano gold particles
for all the
appear in diferent colour. This colour depends on the size of the particle. Not only gold,
materials will show the peculiar behaviour and change in their properties when they enter into the nano
scale. That is why one nanometer is called as a magical point on the dimensional scale.
One example is the "quantum size effect" where the electronic properties of solids are altered
with great reductions in particle size. This effect does not come into play by going from macro to micro
dimensions. However, it becomes pronounced when the nanometer size range is reached. A certain
number of physical properties also alter with the change from macroscopic systems. Novel mechanical
activities also reveal
properties of nanomaterials are a subject of nanomechanics research. Catalytic
new behaviour in the interaction with biomaterials. Thus manipulation of matter at nanoscale provides
some novel properties to the material.

13.3 NANOCHEMISTRY AND APPLICATIONS

make nanoscale building blocks of

Nanochemistry is the utilization of synthetic chemistry to Its target is to
aterent size and shape, composition and surface structure, charge and functionality.
control self assembly of these building blocks at various scale lengths.
based upon individual or multiple
Nanotechnology is concerned with a device, product or process,
integrate nanoscale components.
Applications of Nanochemistry
research. Nanotechnology is
applications of Nanochemistry in industry and
here are numerous
all branches of science and engineering.
-disciplinary subject and it finds applications in almost
Some important ones are listed below:
Fabric: The properties of familiar materials are being changed by manufacturers who are adding
improve performance. For example,
some
nano-sized components to conventional materials to
nano-sized whiskers
clothing manufacturers are making water and stain repellent clothing using
in the fabric that cause water to heat up on the surface.
 520 A TEXTBOOK OF ENGINEERING CHEMISTRY

2. Strength of materials: Nano-sized particles of carbon, for example, nanotubes

are extremely
bucky balbal ls
strong. Nanotubes and bucky balls are composed of only carbor andoky
comes from special characteristics ofthe bonds between carbon atoms. One proposedsengththeir strength
ed
that illustrates the strength of nanosized particles of carbon is the
bullet proof vests made out of carbon nanotubes.
manufacture application
facture oofT-shirt weight
3. Drug delivery: Today, most harmful side effect of treatments such as chemotheran
of drug therapy
delivery methods that don't pinpoint their intended target cell accuratelv. Re.
is a
result
Harvard and MIT have been able to attach special RNA strands,
measuring about tat
diameter, to nanoparticles and fill the nanoparticles with a chemotherapy
are attracted to cancer cells. When the nanoparticle encounters a cancer
drug, These RNA.n
cell it adheree s
releases the drug into the cancer cell. This directed method of
drug delivery has great noa
for treating cancer patients while producing less harmful side effects tential
than those produced
conventional chemotherapy. by
4. Micro/Nano Electromechanical Systems: The ability to create
gears, mirTors, sensor elements
as well as electronic
circuitry in silicon surfaces allows the manufacture of miniature
sensos
such as those used to activate the
airbags in the cars. This technique is called MEMS (Micro
Electro Mechanical Systems). The MEMS
technique results in close integration of the mechanical
mechanism with the necessary electronic circuit on a
single silicon chip, similar to the method
used to produce computer chips.
Using MEMS to produce a device reduces both the cost and
size of the product, compared to similar devices made with
conventional methods. MEMS isa
stepping stone to NEMS or Nano-ElectroMechanical Systems. NEMS products are being made
by a few companies, and will take over as the standare once manufacturers make the investment
in the equipment needed to
produce
nano-sized features.
5. Molecular Manufacturing: Researchers are working on developing a method called molecuar
manufacturing that may be called amolecular fabricator; this device would use tiny
to position atoms and molecules to build an manipulatos
object as complex as a desktop computer. Researchen
believe that raw materials can be used to reproduce almost any inanimate object using this mEn
Two main approaches are used in
In the "bottom-up"
nanotechnology. (i) Bottom-up approach (i) Top-down appreh
approach (synthesizing), materials and devices are built from molec
components which assemble themselves chemically by
principles of molecular recogni
Bottom-up approaches, uses the chemical properties of single molecules to cause lecule

components to (a)
single-n y on
self-organize self-assemble into some useful conformation, or (b) r
or
positional assembly. These approaches utilize the concepts of molecular self-assembly and
molecular recognition. Such bottom-up oduct
abletoprodt
approaches should, broadly speaking, be a be be
devices in parallel and much
cheaper than top-down methods, but could po
overwhelmed as the size and complexity of the desired
assembly increases.
In the "top-down" approach
without

(fabricating), nano-objects are constructed from larger enunarble

atomic-level control. This approach is analogous to bf
making a statute from the h
and is considered as natural extension of current
methods of microelectronics in whiC strucures
of limited dimensions are created by
away

etching
laying down thin layers of material
terial and
and ro-fabrication methods

unwanted parts of each layer. It uses the traditional

workshop or micro-fabrica d shape
lesiredshape

where externally controlled tools are used to cut, mil1, and shape materials into the
and order.
 NANOCHEMISTRY 521
. Miscellaneous Applications:

used in formation of
(a) It is
( Nanooxides of nobel, ferromagnetic and rare metals like Ag, Au, Ti, Zr etc.
and nanopolymers.
(ii) Nanomembranes
in Nanomaterials such as cement, fertilizer, nanopowders, toothpaste, etc.
skincare products, etc.
(iv) Cosmetics, e.g. sunscreen,
and photographic films.
(v) Screens
(vi) Exhaust purification.

(vi) Built in ovens and baking trays.

reactions.
(vii) Catalyst for chemical
the following fields:
6) If finds applications in
) Nano energy application.
(i) Nanogreen chemistry.
(iin) Separating technology for waste water treatment and food production.

TECHNOLOGY
13.4 BOTTOM-UP AND TOP-DOWN APPROACHES IN NANO

Nanostructures or particles can be created by either of the Top Down

two approaches as shown in Fig. 13.1. A tabulated comparison of

Two approaches gives a summary of the two strategies.
Bulk
13.4.1 Comparison of the Top Down and
Bottom Up Processes

Top Down Process Bottom Up Process

Powder
)It involves slicing or Process involves building up
successive cutting of a bulk of a material from the bottom;
material to get nano sized atom by atom, molecule by

particles molecule or cluster by cluster. 4Nano Particle

(i) Attrition or Milling is a Colloidal dispersion is an
typical top down method in example of bottom up
making nano particles. approach in the synthesis of
nano particles.
Clusters
|(üi) Problem of imperfection of Absence of available tools at
surface structure, internal nano scale favours bottom up
stress and significant approach which provides a

cry stallographic damage to better chance to obtain nano

the processed structures with less defects,
patterns
leading to design and more homogeneous chemical
fabrication problems. composition.
Atoms

tm

Fig. 13.1 Schematic representation

of the building up of Nanostructures.
522 A TEXTBOOK OF ENGINEERING CHEMISTRY
Characteristics that a structure should possess by any of the fabrication techni.
(a) ldentical small size of all particles (also called mono sized or with
ith uniform iques
uniform size ditei
(b) ldentical shape or morphology. distribution
(c) Identical chemical composition and crystal structure that are desired among different
and within individual particles, such as core and composition must be the ifferent particles
same.
(d) Particles should be individually dispersed or mono dispersed, i.e., no
agglomeration
Now let us understand some of the important concepts of nano
technology:

13.5 NANOSCALE MATERIALS

Nanoscale materials are materials with a microstructure, the characteristic
length scale of which
is of the order of a few nanometers (1-100). The microstructure refers to the chemical
arrangement of the atoms, and the size of a solid in one, two, or three dimensions. composition, the
Physical electronic or catalytic properties of solids are altered if there is interaction at nano
scale. As mentioned earlier, materials reduced to the nanoscale can suddenly show
very different properties
compared to what they exhibit on a macroscale, enabling unique applications. For instance, opaque
substances become transparent (copper); inert materials attain catalytic
properties (platinum); stable
materials turn combustible (aluminum); solids turn into liquids at room temperature (gold); insulators
become conductors (silicon). Materials such as gold, which is chemically inert at normal scales, can
erve as a potent chemical catalyst at nanoscales. Much of the fascination with nanotechnology stems
from these unique quantum and surface phenomena that matter exhibits at the nanoscale.
Nanomaterials can be constructed by 'top down' techniques, producing very small structures
from larger pieces ofmaterial. For example, to create circuits on the surface of a silicon microchipby
etching. They may also be constructed by 'bottom up' techniques, which means atom by atom or
molecule by molecule.
Although, we categories nonmaterials as those which have structured components with at least
one dimension less than 100 nm. Materials that have one dimension in the nanoscale and are extended
in the other two dimensions are layers, such as a thin films or surface coatings. Materials that are
nanoscale in two dimensions (and extended in one dimensions include nanowires and
nanotubes
Materials that are nanoscale in three dimensions are particles. For example, precipitates,colouds
p of
and quantum dots tiny particles of semiconductor materials.
Nanocrystalline materials, made p
nanometre-sized grains, also fall into this category.
Ihe various classes ofnanoparticles that serve as the building blocks ofnanomaterials and devices

have been discussed below.

13.5.1 Nanocrystals and Clusters

Nanocrystals are crystals of nanometer dimensions, usually consisting of aggregates ota
hundred to ten thousands of atom combined into a cluster. Nanocrystals have typical dimensionso nd
50 nanometers (nm), and thus they are intermediate in size between molecules and bulk
materia
exhibit properties that are also intermediate.

Applications andi n
() Nanocrystals are of great interest because of their promise in high density data storug
electronic applications, as they can be efficient light emitters. Donents,

(i). Nanocrystals have also found applications as biochemical tags, as laser and optical comp
for the preparation of display devices, and
(iii) For chemical catalysis.
 NANOCHEMISTRY 523
Nanocrystalline Materials
3.5.2 Nan

and metal oxide nanoparticles. In the last two decades a class of

T h ose
ese include ceramics, metals,
with a nanometer-s
r-sized microstructure have been synthesized and studied. These materials
building The blocks
aehled from nanometer-sized building blocks, which are mostly crystallites.
areassem

structure, crystallographic orientation, or chemical composition.

their atomic :
differ in
may

oxides
compared to macro-scale materials, nanometals and
Applications

their increased surtace

area as
Due to
)
are ultra-high
activity catalysts.
solid-state
They are also used as desirable starting materials for a variety ofreactions, especially
(i)
reaction.

oxides are also widely used in the formation of nanocomposites.

) Nanometals and
useful and unique magnetic, electric, and optical properties.
(a) They have many
13.5.3 Fullerenes (Gg0)
carbon, in the
allotropes, i.e., molecules composed entirely
of
Fullerenes are family of carbon
called buckyballs, and
hollow spare, ellipsoid, tube or plane. Spherical fullerenes are also
fom of a
an example of a planar
ones are called carbon
nanotubes or buckytubes. Graphene is
cylindrical atoms that are densely
fullerenes sheet. Its structure is one atom
thick planner sheets of Sp>-bonded C
nanotubes (or silicon nanotubes),
in honeycomb crystal lattice. These include the carbon
packed a
of their electrical
mechanical strength and also because
which are of interest both because of their
properties.
sheets of hexagonal rings,
Fullerenes are similar in structure to graphite, which is composed of
but may also contain pentagon rings.
by formed interconnecting six-
Fullerenes are elongated sphere of carbon atoms
defined as an
and pentagonal faces. The first isolated
ember rings and isolated five-member rings forming hexagonal
faces and 12 pentagonal faces just like a
soccer

ndcharacterized fullerene, Co, contains 20 hexagonal

ball and possess
perfect symmetry.

lattice
Fig. 13.2 (a) Buckminsterfullerene Co (b) Graphene
 524 A TexTBoOK OF ENGINEERING CHEMISTRY

Development of different varieties of Fullerenes

Since
the discovery of fullerenes in
development of many variety such as:
1985, structural variations on
fullerenes have iled
fullerenes
to the
()Buckyball clusters: They are the smallest members with 20 carbons, comparable to unsatiw
dodecahedrane and the most common is C-20. aturated
(ii) Nanotubes: They are hollow tubes of very small dimensions, having single or
multinle
and have potential applications in electronics industry. walls
(iii) Megatubes: They are larger in diameter than nanotubes and have walls of different thickna.
These are potentially used for the transport of a variety of molecules of different
sizes,
kness
(iv) Polymers: Two-dimensional and three-dimensional polymers are formed under
high presqia
d high temperature conditions.
() Nano "opions": They are spherical particles based on multiple carbon layers surroundineg:
bucky'ball core. They are used as lubricants.
(7) Hydrated fullerene (HyFn): Hydrated fullerene
CoHyFn is a stable, highly hydrophilic, supra-
molecular complex consisting of C6o fullerene
molecule enclosed into the first hydrated shell that
contains 24 water molecules: Cgo @ (H,O)24. This
hydrated shell is formed as a result of donor-acceptor
interaction between lone-electron pairs of oxygen,
water molecules and electron acceptor centres on
the fullerene surface. Meanwhile, the water
molecules which are oriented close to the fullerene Fig. 13.3 CoHyFn water solution with
surface are interconnected by a three-dimensional a C6o Concentration of 0.22 g/l
network ofhydrogen bonds. The size of CHyFn is 1.6-1.8 nm. The maximal concentration of
Cso in the form of CHyFn achieved by 2010 is 4 mg/mL.
Fullerite: Fullerites are the solid-state manifestation of fullerenes and related compounds
(vii)

materials. "Ulrahard fullerite" is a coined term frequently used to describe material produced by
and
high-pressure high-temperature (HPHT) processing of fullerite. Such treatment converts tulenir
into a nanocrystalline form of diamond which has been reported to exhibit remarkable mechan
properties.

Characteristics of Fullerenes
(i) They are insoluble in water, but soluble in organic solvents. C-60 is soluble in benzeneapui
can

be crystallized from it.

(i) They exhibit excellent tensile strength and very high packing density.
ponsible
(ii) C-60 is non-toxic and a powerful antioxidant. In living cells, it reacts with free radicalsrespo
for the damage.
(v) They possesses cage like structure
(v)They are impermeable to all elements under normal circumstances.
(vi) C-60 crystal is an insulator but when dopped with an alkali atom, it becomes conducting
(vi) C-60crystal doped with potassium becomes superconductor at 15SK.
 NANOCHEMISTRY 525
Applications of Fullerenes

Fullerene chemistry continues to be an exciting field generating many articles with promising

new applications every year. Some examples are given below:

(Magnetic nanoparticles show great potential for high-density magnetic storage media.
C-60 dispersed into ferromagnetic materials such as iron, cobalt can form thin films with promising
magnetic properties.
in A number of organometallic-fullerene compounds have recently been synthesized which are
being used in industry.
()Some fullerene derivatives even exhibit superconducting character. There has been a report of a
fullerene containing, superconducting ficld-effect device with a Te as high as 117 K.
()Fullerenes are used as miniature ball bearings for lubrication.
(1) They can be used as drug deliverers by the attachment of functional ligands to their carbon cage.
(vii) They can be used as tracers molecules by trapping lanthanide metals inside their cage.
(vi~) They are useful in fighting the HIV virus that leads to AIDS.
(ix) They are impervious to lasers and can be used as defensive measures in war

13.5.4 Carbon Nanotubes (CNTs)

Carbon nanotubes are hollow cylinders of carbon atoms. Their appearance is like rolled tubes of
graphite. The ends of CNTs have domed structures of six-membered rings capped by a five-membered
ring. Carbon nanotubes (CNTs) were first isolated and characterized by ljima in 1991.
There are two types of CNTs: Single-walled carbon nanotubes (SWNTs) and multi-walled carbon
nanotubes (MWNTs). As their names imply, SWNTs consist of a single, cylindrical graphene layer,
where as MWNTs consist ofmultiple graphene layers fused into one another. A large numberofarticles
have been published on CNTs and many new applications of CNTs are
emerging every year.
Characteristies of Carbon nanotubes
The
has unique physicaland chemical properties of CNTS, such as structural rigidity and flexibility
increased their utility. Their important characteristics are given below:
(1) CNTs are extremely strong, about 100 times stronger than steel.
(ii) CNTs can also act as either conductors of semiconductors
depending
on their chirality.
ii) They can act as superconductors, and can also behave as field emitters.
They possess very low density about half of density of aluminium metal.
) They possess high elasticity and high thermal conductivity almost twice as that of diamond.
(4) They have high current
density and high aspect ratio i.e., length to diameter ratio.
Applications
0)
Carbon nanotubes are now the
top candidates to replace silicon based semiconductors as
nave variable semiconducting properties with energy gaps ranging from a few milli electron they
volt
(meV) to a few tenths of an electron volt (eV).
(i) Nanotubes have led to a new
n) Their use as
generation of electronic devices.
ultra-sensitive electromechanical sensors has also been
explored.
They are used in
designing of
field-effect transistors (FETs) and integrated
electronic devices.
They are used in designing chemical and radiation sensors.
(Vi) They are used in composites and mcnufacture offuel cels.
 526 A TEXTBOOK OF ENGINEERING CHEMISTRY

13.5.5 Dendrimers (Organic Nanoparticles)

Dendrimers are macromolecules having special structure and can be classified as a snoni.
pe
of polymers. These nanometer sized. polymeric systems are hyperbranched materials. The e
dendrimers has many chain ends which can be utilized to perform diferent chemicalfunctions T
may be water-soluble but, because of their compact dimensions, they do not have the usual thicken They
properties that many polymers have in solution. Dendrimers are composed of three components:
(i) A central core
(ii) An interior dendritic structure (the branches), and
(il) An exterior surface (the end groups).
Over 50 families different in composition and structure of these nanoscale macromolecules a
are
known.
Characteristics of Dendrimers
() They are characterized by nearly spherical structures of nanometer sizes.
(ii) They have large numbers of reactive endgroups.
(i) They contain interior cavities into which other molecules could be placed and are thus used in
drug delivery.
(iv) They have low toxicity.

Applications of Dendrimers
) Due to their specific properties they are used in nanotechnology applications in both biological
and materials sciences.
() They find applications in many fields, including material engineering, industrial, pharmaceutical,
and biomedical applications.
(ii) They are used as manoscale catalysts and novel lithographic materials.
(iv) They have been used in many fields such as targeted drug delivery systems,. magnetic resonane
imagine (as contrast agents), and bioadhesives.

13.5.6 Nanocomposites
Nanocomposites are materials with a nanoscale structure that improve the macroscopic propei
of products. Typically, nanocomposites are clay,
polymer or carbon, or a combination of these maena
with nanoparticle building blocks. Nanocomposites, materials with nanoscale separation of phases can
generally be divided into two types:
() multrilayer structures which are formed by gas phase deposition or from the self-assembly ot

monolayers.
(ii) inorganic/organic composites which can be formed by sol-gel techniques, bridging De tween

clusters, or by coating nanoparticles, in polymer layers.

Applications of Nanocomposites
evel
() Nanocomposites can greatly enhance the properties of materials. For example, ppm le
impurities in aluminum alloys, increase their strength and corrosion resistance.
as
ii) Magnetic multilayered materials are one of the most important aspects of nanocompos
they have led to significant advances in storage media.
 NANOCHEMISTRY5 2 7
13.5.7 Biological Nanomaterials
The materials of biological origin are referred to as biological materials. These are used for
notechnogical applications. These materials comprised of biological molecules and have specific
lication which belong to proteins, nucleic acids, lipids, hormones, vitamins etc. Biological
materials show properties such as: Self-assembling properties and specific molecular recognition.

Nanomaterials
Applications of Biological
( Biological nanomaterials are used for specific filtration and drug delivery.
used as sensors, motors and actuators.
(ii) They are
(in) They are also used in arrays (chips) for large scale protein or DNA screening.
in devices.
(iv) These materials find application the formation of memory
13.5.8 Nanowires
Nanowires are ultrafine wires or linear arrays of dots, formed by self-assembly. They can be
made from a wide range of materials. Semiconductor nanowires made of silicon, gallium nitride and
indium phosphide have demonstrated remarkable optical, electronics and magnetic characteristics.

Applications of Nanowires
Nanowires have potential applications in high-density data storage, as magnetic and electronic
nanodevices.
(ii) The nanowires can be used in Chemical Vapour Deposition (CVD) technique.

13.6 FUTURE PROSPECTS OF NANOTECHNOLOGY

The impact of nanotechnology is expanding and nothing will remain untouched by this field in
the near future. Its applications are enormous and limitless. Nanotechnology enables us to do things
better than conventional technology. Nanotechnology is sure to revolutionise the most demanding fields
of the present age namely:
1. Computer and electronic 2. Medicines 3. Pollution control
For example, there are enormus applications in computers to increase memory and speed. It is
said that computers will run fast, medicines will cure all diseases, and pollution could be eliminated
with the application of nanotechnology. The applications are immense, and it is predicted that
nanotechnology will revolutionize the industrial world in the 21st century. The following are the major

Sarcas, which are developed by nanochemistry, for the benefit of future generation.
being
)Surface coatings consisting of nanomaterials become scratch proof, weather proof, more
durable, better shining and dirt repellant.
(i) Nanotechnology can enable drugs to destroy cancer or tumor without any side-effects.
(ii) Nanotubes pacemakers placed in the heart blood vessels could generate electricity for heart
function.
(iv) Nanosized robots can repair damaged and diseased tissues.
(v) Converting sunlight into power, cleaning the pond water for drinking.
(vi) Creating sensor in the form of biochips to tbe planted in human body.
 OF ENGINEERING
CHEMISTRY
528 A TExTBOOK

sunscreens, creams, and lotions. whi

(vii) Nanosized titanium dioxide is used in cosmetic,
more durable.
ome
(vii) Nano impregnated clothes can block chemical and biological weapons from touu

skin.
(ix) Nanotechnology can help to detect narcotics and finger prints of criminals.
(x) Nano assembled monolayer could be coated on to the fibres of the cloths so that
that iit does not
attract dirt and becomes self-cleaning and germ
free.
The future prospects of nanotechnology are very bright, as it directly concerns the quality, com
and better health of the masses. Lot of academic institutions, Research and Development labs and
and
industries are likely to come up. Government of India is promoting focused programmes
in
nanotechnology and huge funds are being allocated to scientific departments for growth ofnanosciences

INFORMATION WINDOW

Nanochemistry
1. The term nano means one billionth or 10 of a meter.
2. Nano chemistry is the study of fundamental principles of molecules and structures with at least
one dimension roughly between 1 and 100 nanometers.
3. Nano scale is defined as to be from 100 nm down to the size of atoms because of thin scale
properties of material can be different from those of a larger scale.
4. Due to increased relative surface area and quantum effects the properties ofnanomaterials changer
drastically.
5. Nanochemistry is also utilization of synthetic chemistry building blocks, of different size and
shape, composition and surface structure, charge and functionality.
6. Nanochemistry finds applications in almost all branches of science and engineering for eg. n
fabrics, strength of materials, drug delivery, micro/nano electromechanical system, molecular
manufacturing etc.
7. Top down" approach is fabricating nano-objects from
large entities without atomic level control
up" approach
"Bottom is used for synthesis in which materials and devices are build from
molecular component.
9. of
Nano-crystals
a
crystals of nanometer dimensions (of I to 50 nm) consistingof aggregates
are
few hundred to ten thousands of atoms combined to cluster.a
10. Nano-crystals finds
application in high density data storage, as efficient light emitters
11. Due to increased surface area as compared to macro-scale nano-metals and oxides areultra-
tra-high
activity catalyst.
12. Nanometals and oxides are widely used in the formation
of nanocomposites. rical
13. Fullerenes carbon
are allotropes. Spherical fullerenes are also called bucky balls and
ones are called carbon nanotubes or
cylinan
bucky tubes. comb

14. defined as an elongated sphere

Fullerenes are
crystal lattice.
ofsp
carbon atoms, densely pocked in a honeyeo
15. isolated and characterized fullerence Co contains 20 hexagonal faces and 12 pentag
First
faces.
16. Bucky ball clusters are smallest members with 20 carbons. Nanotubes are hollow Iuoonics
small dimensions having single or
multiple walls and have potential applications in c
industry.
 NANOCHEMISTRY 529

17 Hydrated Fullerence: C6oH,F, is a stable, hydrophilic, supra-molecular complex consisting of

C fullerene molecule enclosed into the hydrated shall containing 24 water molecules.
Carbon nanotubes (CNTs) are hollow cylinders of carbon atoms appeared like rolled tubes of
18
graphite
19 Dendrimers are macromolecules classified as special type of polymers. They are nanometer
sized, polymeric systems are hyperbranched materials.
20. Dendrimers used in nanotechnology applications in biological and material s
are

21. Nano-composites are materials with a nanoscale structure that improve the macroscopic properties
of products.
22 Biological nanomaterial comprises biological molecules like proteins, nucleic acids, lipids.
hormones, vitamins etc. These are used for drug delivery, sensors, motors and actuators, used in
arrays (chips) for large scale protein or DNA screening.

PROBLEM WITH sOLUTIONS

Problem 1. What do you mean by NANO?

or 10 of
Solution. The term nano means one billionth of a unit. One nanometer (nm) is one billionth,
a meter. It is comparable, typical with carbon-carbon
bond lengths, or the spacing between these atoms
in a molecule, are in the range 0.12-0.15 nm, and a DNA double-helix has a
diameter around 2 nm. On
are around 200
the other hand, the smallest cellular life-forms, the bacteria of the genus Mycoplasma,
nm in length.
Problem 2. Define NANO TECHNOLOGY.
atomic and molecular level having scale
Solution. It is the technique of manipulating the matter on an

and size in the nanometer range.

Problem 3. Define NANO SCIENCE.

material
Solution. It is the study of relationship between various phenomena, physical properties and
dimensions at nano scale.
Problem 4. What is the difference between NANO SCIENCE AND NANO TECHNOLOGY?

is that the former is

Solution. The important difference between nano science and nano technology
and material
related to the study of relationship between various phenomena, physical properties behind
nano structures and principles
nano scale, whereas later is the application of these
aimensions at
them to make nano scale devices and materials.

Problem 5. What is top down approach in nanotechnoloEy?

constructed from larger entities
Solution. In the "top-down" approach (fabricating), nano-objects are

without atomic-level control.

Problem 6. What is botom up approach in nanotechnology?
Olution. In the "bottom up" approach (synthesizing), materials and
devices are built from molecular
ponents which assemble themselves chemically by principles of molecular recognition.

Problem 7. Define nano structured material?

and principles behind them is
ution. A material produced with the application of nano structures
aCd nano structure material. This type of material has shown some novel properties.
 ENGINEERING CHEMISTRY
S30 A TEXTBOOK OF
term self assembly?
Problem 8. What do you understand by the
in which disordered system of system of preexisting
Solution. The term self assembly refers to the process .

specific local interactio

components forms an organized pattern
structure or
external
as a result of

force or direction.
interaction among the
constituent components without any

Problem 9. Classify nanomatrials and give examples for them?

Solution. Generally nanomaterials are categorized as : fullerenes, and inorganic nanoparticles C
and of fullerene and nanocrystals (say of Cu) and nanoclusters and rnapene
buckyball are examples
are some of the examples of inorganic nano particles.
opowder
Problem 10. What are nano composites? Classify nanocomposites.
Solution. A nanocomposite is formed as a result of self assembly. Nano composite is a term use for
multiphase solid material, in which one, two or more dimensions have nano size particles. Depending
upon number of dimensions of nano scale these can be classified as zero dimension called cluster one
dimension called wires/tubes, two dimensions sheets/colloids and 3-dimension complex shapes.

Problem 11. List any four day to day live commercial applications of nanotechnology?

Solution. Application of nanotechnology is to drug delivery, fabric technology, augumenting materal

strength, nano electromechanical systems.

Problem 12. Write down any three challenges that are faced by researchers in nanotechnology?

Solution.
1. Overcome the huge surface energy, a result of enormous surface area or large surface area to

volume ratio.
2. Ensure all nanomaterials with desired size, uniform size distribution, morphology, crystaliniy
chemical composition, and microstructure, that altogether result in desired physical propertes
3. Prevent nanomaterials and nanostructures from coarsening through either Ostwaldnipen
or agglomeration as time evolutes.
Problem 13. What do you mean by quantum dots and nanocrystals?
Solution. Quantum dots (QD) or semiconductor nanocrystals are a form of light emitting techno

and consist of nano-scale crystals that can provide an alternative for applications sucn aelated
f oto
technology. Quantum dots are semiconductors whose electronic characteristics are closeiy i
the size and shape of the individual crystal.
there
Problem 14. What is the diameter of a buckyball? How many pentagons and hexagons
in a bucky ball?
world

Solution. Cs molecule has a molecule diameter of 7.10A. The roundest known molecule inic
the Buckyball has carbon atoms at 60 chemically equivalent vertices that are connected by
of which are pentagonal and 20 hexagonal.

Problem 15. What for MEMs stands for?

in silicon
Solution. The ability to create gears, mirrors, sensor elements, as well as electronic circunuye in the
surfaces allows the manufacture of miniature sensors such as those used to activate the au
car. This technique is called MEMS
(Micro-ElectroMechanical Systems).
 NANOCHEMISTRY 531
16. What are the types of carbon nanotubes?
Deablem
ro
and multi
alation. There types of nanotubes namely single walled carbon nanotubes (SWNTs)
are two
olu
SWNT consists only of a single graphene sheet with one atomic
led carbon nanotubes (MWNTs).
thickness, while MWNT is formed
from 2 to several tens of graphene sheets arranged
in
into tube structures.
concentrically
area of nanoparticles?
What the effects due to increase in surface
Prablem 17.
decreases
size reduces from centimeter (bulk) to nanometer scale, properties mostly
Solution. As material level. The reason for this change is due to the nature
orders of magnitude to that at macro
asmuch as six out of existence in the bulk material. The same can be
the atoms that are averaged
of interactions among overall surface area which in turn
i.e., surface energy increases with the
explained in another way are having reduced dimensions, it
the dimension of material. As
nanostructures
strongly depend on
surface via increase in surface area.
energy
leads to increase in

carbon nanotube.
Problem 18. Define
walls. These are cylindrical
small dimensions, having single or multiple
Solution. Hollow tubes of very but they can range from
of carbon and is usually only a few nanometers wide,
fullerenes. It comprises
less than a micrometer to several millimeters in length.

Problem 19. Define bucky ball.

fullerenes and they resemble the balls used in association football.
Solution. Buckyballs are Spherical

REVISION QUESTIONS

Nanoscale materials? What makes

the nano-material unique?
1. What are

2. What are fullerenes? Explain with examples.

materials:
3. Write short notes on the following nanostructured
(b) Nanocrystalline materials
clusters
(a) Nano-crystals and (d) Biological Nanomaterials
(c) Dendrimers nanotools.
nanotube based devices and
4. What are carbon nanotubes? Explain with examples
5. Write short notes on:
(b) Nanowires
(a) Nano composites
of nano-materials.
6 What are Nano-materials? Give examples of five categories
for the development
What is Nanochemistry? Outline some future prospects ofnanotechnology
of industrial products.
characteristics and list some of their applications.
8 What are the Fullerenes? Give their types,
9 Write notes on:
(b) Carbon nanotubes
(a) Fullerenes
10. Write short notes on the following:
(b) Carbon nanotubes
(a) Fullerenes
c) Nanocomposites