1

UNIT-V
NANO CHEMISTRY
5.1.INTRODUCTION
Knowledge and use of nano particles were known for a long time. Its scientific study and
applications in various fields are of recent orgin. Nano science is a broad term which includes
nanomaterials, nanoparticles, nanochemistry, nanophysics, nanoelectronics, nanomedicine and
nanotechnology. The important significance of nanoscience lies in its far and wide applications in almost
all the branches of science.
Nano-, a prefix denoting a factor of 10
-9
has its orgin in the Greek work word nanos, meaning
dwarf. The term often used with time interval of a nano second, a billionth of a second and the length
scale of nanometer or 10 . Broadly nanoscience and technology deals with the visions of making,
manipulating and utilizing really small things to do big things.
The royal society has defined nanotechnology as the design, production characterization and
application of systems, structures and devices of nano meter size.
In recent years, Nanotechnology has become one of the most important and exciting forefront
fields in physics, chemistry, biology and engineering. It shows great promise for providing us with many
breaks through in the near future. This will change the direction of technological advances in a wide range
of applications.
5.2.DEVELOPMENT OF NANOTECHNOLOGY
It is not clear when human began to take advantages of nano size materials.
1) It is known that in 400 AD, Roman glass makers were fabricating glasses containing nano size
metals.
Lycurgus Cup, glass, 4th century, Roman. Nanoparticles (70 nm) of gold and silver, dispersed in
colloidal form, are responsible for the dichroic effect (red/green).
2


Figure.5.1.Lycurgus cup
2) In 1661, Robert Boyle a very famous chemist recognized the importance of Nano clusters.
3) In 1857, Michael Faraday explained how metal nano particles affect the colour of church
windows.

Figure.5.2.Medival church windows
4) Zsigmondy was the first person to observe and measure the dimensions of nano particles.
5) In 1920, Langmuir introduced the concept of monolayer of nano dimensions.
6) Uhelir reports the first observation of porous nano sized silicon in 1956.
7) Richard Feynman was awarded Noble Prize in physics in 1966. He proposed his idea of utilizing
the surface are of materials under nano scale. He delivers a famous lecture There is plenty of
room at the bottom. He recognized the existence of nanostructures in biological systems.
8) Nano sized magnetic fluids called Ferro fluids were developed in 1966. They have a number of
interesting properties and applications.
9) Structural features of metal nanoparticles such as the existence of magic numbers were revealed
in 1970.
10) In 1986, Drexler introduced the term Nanotechnology in his book Engines of creation
11) First nano medicine book was published in 1999.
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12) Richard E. Smalley was known for the discovery and characterization of C- 60 Bucky ball in
2000.
13) The National Nanotechnology Initiative was created in U.S.A. This provides fund for
nanotechnology research i.e., Billion dollars per year.
14) From 2005, almost all industries in the world have dramatically changes by nano-technological
applications.
5.3.SIZE DEPENDENT PROPERTIES
COMPARISON OF NANO MATERIALS WITH BULK MATERIALS AND MOLECULES
Many properties of solids depend on their size. At the macro or large scale range, ordinarily
studied in physics such as mechanics, electricity, magnetism and optics, the size of the objects range from
millimeter (110
-3
m) to kilometer (110
3
m). Their properties are the average properties.
When the measurements are made in micro meter (110
-9
m) range, i.e., the nano materials have
entirely different properties. These are given in the following table.
Table 5.1 Comparison of nano materials with bulk materials.
S.No. Property / Materials Nano Materials Bulk Materials
1 Size 1 to 100nm 1 to 10 micron
2 Formation By few molecules By more than 1000 molecules
3 Surface are Very High Low
4 Ductility High Low
5 Strength, Hardness &
Toughness
Very High Low
6 Corrosion resistance High Low
7 Wear resistance High Low
8 Density Low High
9 Melting Point Low High
10 Sintering time Low High
11 Thermal conductivity Low High
12 Electrical conductivity Low High
13 Elasticity Low High
14 Properties Depend on size Do not depend on size
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15 Iron, Nickel Super paramagnetic Ferro magnetic
16 Sodium, Potassium Ferro magnetic Para magnetic
17 Chromium Paramagnetic Anti Ferro magnetic
18 Colour of Gold Deep red to black Yellow

The manner, how the above different properties vary in the nano materials, is shown in the
following flow diagram.

Surface area
Ductility,
Strength
Hardness
Toughness
Corrosion resistance, wear resistance
Density
Melting point
Thermal and electrical conductivity
Elasticity

Figure.5.3.Properties of nanomaterials
A part from these, a number of mechanical, electrical and optical properties of nano materials are
changed drastically when compared to macroscopic systems.
Table.5.2. Difference in properties of molecules, nanoparticles and bulk materials
S.No. Molecules Nanoparticles Bulk materials
1. It consists of mostly two
atoms.
It consists of one or two or
three dimensional
arrangements of few
atoms.
It consists of three
dimensional
arrangement of a large
number of atoms.
2. Their properties are size
independent.
Their properties of size
independent.
Their properties of size
independent.
3. Their sizes are smaller than
nanoparticles and bulk
Their sizes are intermediate
between molecules and
Their sizes are larger
than molecules and
Nano materials
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materials. bulk materials. nanoparticles.
4. Their sizes are expressed in
angstrom (A) unit.
Their sizes are expressed in
nanometer (nm)unit.
Their sizes are expressed
in millimeter unit.
5. Their electronic structure is
confined.
Their electronic structure is
confined.
Their electronic
structure is continuous.
6. They have well defined
geometrical structure.
They have well defined
geometrical structure.
The nature of bulk
material decides the
geometrical structure.
Examples







5.4.DIFFERENT FORMS OF NANO MATERIALS
1. Nanomaterials, in zero dimensions, are nano clusters and nano spheres.
2. Nanomaterials, in one dimension, are layers such as thin films, surface coatings.
3. Nanomaterials in two dimensions are tubes such as Nanotubes and Nanowire.
4. Nanomaterials, in three dimensions, are particle like precipitates, colloids and quantum dots.
TYPES OF NANOMATERIALS.
5.4.1.Nano-particles
1. Nanoparticles are the particles that have three dimensional nano scale.
2. Their size is between 1 and 100 nm in each spatial dimension.
3. They exhibit better physical, chemical and mechanical properties than the bulk materials.
4. They are very tiny aggregations of atoms.
5. They are bigger than molecules and smaller than their crystals.
Examples: Ag, Au, TiO
2
, ZnO, CaO, CdS, liposome, fullerene.
Applications of nanoparticles
A. Nanoparticles of TiO
2
are
(a) used in cosmetics as moisturizers.
(b) used as a brilliant white pigment in paint.
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(c) used in sun screens as uv-absorber.
B. Nanoparticles of silver are
(a) used as catalysts in chemical industries.
(b) used as anti-bacterial and anti-fungal agents in biotechnology.
(c) used for making bone cement, surgical instruments, surgical masks and wound dressings.
C. Nanoparticles of liposome is used to deliver tiny doses of medicines directly into cells.

5.4.2.Nanoclusters or nanospheres
1. Nanocluster is the smallest sized nanomaterials because of its close packing arrangement of
atoms.
2. It is an example of zero dimensional nanomaterials.
3. Their size ranges from 0.1 nm to 10 nm.
4. They are the intermediate state of matter between molecules and bulk materials.
5. They are the fine aggregates of atoms or molecules.
6. They are bound by forces like- metallic, ionic, covalent, hydrogen bond, weak van der Waals
forces.
There are two types of Nanoclusters-
(a) consisting of upto hundred atoms
(b) larger aggregates containing 1000 or more atoms

Magic number
It is the number of atoms in the clusters of critical size with higher stability.
Production of Nanoclusters
Nanoclusters can be produced using both bottoms up and top down methods.
Examples: ZnO, SiO
2
, CdS.
Properties
1. They have properties and structures which are very sensitive to their composition and size.
2. They have more confined electronic structures.
3. Their melting point is lower than the bulk materials.
Applications
1. They are of technological interest in numerous areas of applied science.
2. They are used as catalysts in various organic synthesis.
5.4.3.Nanorods
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Nano materials having long sticks or rod shapes with diameter in nanoscale and length very much
longer are regarded as Nanorods.
In other words , it is the materials having an aspect ratio (i.e., length to width ratio) in the range 1
to 20 with short dimension of the materials being 10 to 100 nm.
Production of Nanorods
Nanorods are produced by direct chemical synthesis.
A combination of ligands act as shape control agents and bond to different facets of the
nano rods with different strength.
Examples: ZnO, Au Nanorods
Properties
1. They are one dimensional materials.
2. They show good optical and electrical properties.
Applications
They are used in
(i) Display technologies
(ii) Energy harvesting
(iii) Light emitting devices
(iv) Cancer therapy
(v) Micro electro mechanical systems (MEMS)
(vi) Photoluminescence devices.
5.4.4.Nanowires
They are also called quantum wires.
It is the material having an aspect ratio (i.e., length to width ratio) greater than 20.
They can be used to link tiny components into extremely small circuits.

Types of Nanowires
(a) metallic Nanowires - Ni; Pi; Au
(b) Molecular Nanowires - DNA
(c) Inorganic Nanowires - Mo
6
S
9
I
(d) Insulator Nanowires - TiO
2
; SiO
2

(e) Semiconducting Nanowires - Si; InP; GaN
Production
Nanowires are produced by
(a) Suspension
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(b) vapour deposition
(c) electro chemical deposition
(d) VLS (Vapour - Liquid solid)
(e) ion track technology
Properties
(a) They are one dimensional materials.
(b) They shows strong photoluminescence property.
(c) Their conductivity is less than the bulk materials.
(d) They exhibit distinct thermal, optical and chemical properties.
Applications
1. Semiconducting silicon Nanowires are used for sensing proteins and chemicals.
2. They can be used to build the next generation computing devices.
3. They are used to enhance mechanical properties of composites.
4. They are used to prepare active electronic components like p-n junctions and logic gates.
5. Silicon Nanowires are used to fabricate (Field Effect Transistor) FET based chemo/ biosensors.
5.4.5.Nanotubes
A nanotubes is a nanometer scale tube like structure with diameter of 1 to 100 nm and a length of
few nm to 1000 nm (or microns)
It consists of tiny cylinders of carbon in CNT.
Examples
(i) Human hair is an example of natural nano tube
(ii) Carbon nanotubes (CNT)
(iii) Silicon nanotubes (SNT)
(iv) Boron nitride nanotubes
(v) DNA nanotubes
(vi) Inorganic compounds
(vii) Membrane
Applications
They find use in various fields. Few of them are-
(i) electronic (ii) data storage
(iii) energy production (iv) drug delivery
(v) aerospace (vi) automobile industry
(vii) artificial muscle (viii) nanolithography
(ix) doping (x)waste recycling
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(xi)solar energy storage (xii)hydrogen storage
We shall study CNT in details.
5.5.CARBON NANO TUBES (CNT)
5.5.1.Introduction
Carbon Nano Tubes (CNT) were first observed in 1991 by guo and coworkers. These are
the allotropes of carbon, i.e graphite. When graphite sheets are rolled into a cylinder having
their edges joined, they form CNTs as in the figure. They have the length to diameter ratio,
110
6
. They are produced several tons per year.

Figure.5.4.Allotropies of carbon
5.5.2.Types of CNTs
Based on the number of layers, the CNTs are classified as Single walled Nano
Tubes(SWCNT) and Multi walled Nano Tubes(MWCNT)

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Figure.5.5.SWCNT(a) and MWCNT (b)
Three types of SWNTs are known. These are obtained by rolling a graphite sheet about the axis. They are
(a) Arm Chair structure.
(b) Zigzag structure.
(c) Chiral structure.


Figure.5.6.Different types of single walled carbon nano tubes
5.5.3.Production of CNTs
(i) Pyrolysis of hydrocarbons
(ii) Carbon are method.
(iii) Laser evaporation method
(iv) chemical vapour deposition method
1. CNTs are produced by the Pyrolysis (heating) of hydrocarbons such as acetylene at 700C in the
presence of iron silica catalysts under insert conditions.
2. In Carbon are method, direct current are of 100 A and 25 V is applied between graphite
electrodes of 20 mm diameter.
3. In Laser evaporation method, a quartz tube contains the graphite target. This is kept inside of a
high temperature muffle furnace. This tube is filled with argon gas. It is heated to 1200C. A
water cooled copper collector is fitted at the other end of the tube. The target graphite contains
small amount of nickel and cobalt as catalyst. CNTs are deposited on copper collector.
5.5.4.Properties of CNTs
1. CNTs are very strong and withstand extreme strain and tension.
2. The atoms in CNTs are continuously vibrating.
3. It has high conductivity and behaves like metallic conductor.
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4. It has very high thermal conductivity which is 10 times grater than metal.
5. It has kinetic properties.
6. youngs modulus of CNTs 10 times larger than steel.
5.5.5 Applications of CNTs
1. CNTs used in battery technology and fuel cells.
2. They are used as catalysts in industries.
3. CNTs are inserted inside the body for drug delivery.
4. They are used in composites and ICs.
5. CNTs are used as light weight shielding materials for protecting electronic equipments.
6. They are used to manufacture boat hulls and sport goods.
7. They are used in desalination and to filter CO
2
from power plant emission.
5.6.SYNTHESIS OF NANOMATERIALS
The following two process are used for the synthesis of nano-materials.


Figure 5.7. Synthesis of nanomaterials[Top down and bottom up approach]

(i) Top-down process or physical method or hard method or big to small method.
(ii) Bottom-up process or chemical method or soft method or small to big method.
We shall study them in detail.

5.6.1. Top- down process
Definition
The conversion of bulk materials into nano-scale particles is called top-down process.
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This can be achieved by
(a) Laser ablation
(b) Electro deposition
(c) Chemical vapour deposition
Advantages
1. This method is very easy for manufacture.
2. This involves the breaking of covalent bonds to form
Disadvantages
1. It is a costly method.
2. It takes long time.
3. It is not suitable for large scale production.
5.6.2.Bottom up process
Definition
Building up of atom by atom to produce nano-materials is called bottom up process.
This process is carried cut by
(a) Precipitation
(b) Thermolysis
(c) Hydrothermal process
(d) Solvothermal process
Nano tubes, nanowires, Nanorods etc. are prepared using this process.
Advantages
1. The method is cheap.
2. It allows smaller geometries.
3. It can make films and structures much easier.
4. It does not waste any materials during production.
5. CNT, Silicon Nanowires and organic semiconductors are produced using this process.

5.7.PRODUCTION OF NANOMATERIALS
The following chapters mainly about the synthesize of nanomaterials.
5.7.1. PRECIPITATION METHOD
This is the most useful method of synthesis of nanomaterials.
Several types of reducing gents are used for the preparation.
Examples:
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(A) Nanoparticles of molybdenum can be produced in toluene solution with NaB(C
2
H
5
)
3
H as reducing
agent at room temperature
2MoCl
3
+ 6NaB(C
2
H
5
)
3
H 2Mo + 6NaCl + 6B(C
2
H
5
)
3
+ 3H
2

It gives a high yield of nanoparticles having dimensions of 1 to 5nm.
(B) Nanoparticles of aluminium can be made by decomposing (CH
3
)
2
C
2
H
5
NAlH
3
in toluene and heating
the solution to 105C for two hours.
(C) BaSO
4
nanoparticles are produces in the following way.
In a 250 ml breaker, 10 g sodium hexameta-phosphate (calgon, stabilizing agent) was
dissolved in 80 ml distilled water with constant stirring. 10ml 1M sodium sulphate solution and 10 ml
1M barium nitrate solution were added with constant stirring. The resulting solution was stirred for
one hour and was then allowed to stand for few hours.
Ba(NO
3
)
2
+ Na
2
SO
4
2NaNO
3
+ BaSO
4

The resultant nanoparticles as precipitate was filtered, washed with distilled water and dried in
vacuum.

Figure.5.8.Prepcipitation method
5.7.2.THERMOLYSIS
Thermolysis is the process of decomposing solid at high temperatures having metal cations and
molecular anions or organometallic compounds in the presence of a stabilizing agent. Lithium
nanoparticles can be obtained by decomposing lithium azide, LiN
3
.
2 LiN
3

2 Li + 3 N
2

Method
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Figure.5.9.Thermolysis method

LiN
3
is placed in an evacuated quartz tube and heated to 400C. At about 370C, LiN
3

decomposes releasing N
2
gas. An increase in pressure is noticed in vacuum gauge. In a few minutes, the
pressure drops back to the original value. This indicates the complete removal of nitrogen. The remaining
lithium atoms form small colloidal nanoparticles of 5 nm size. Passivation is called out using an
appropriate gas.
5.7.3.HYDROTHERMAL PROCESS
This process involves the use of water as solvent under high pressure and temperature in a sealed
tube. It is performed below the super critical temperature of water (374C). Aqueous aluminate and
silicate precursors in the presence of base undergoes poly-condensation to form sodium aluminosilicate
gel that under hydrothermal reaction conditions crystallizes into a microporous sodium aluminosilicate
zeolite with water imbibed within the microporous.
NaAl(OH)
4
(aq) + Na
2
SiO
3
(aq) + x NaOH(aq) Na
x
(AlO
2
)
x
(SiO
2
)
y
.zH
2
O (s)

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Figure.5.10.Hydrothermal method
This method is also used to synthesis carbon nanotubes and metal oxide nanoparticles (ZnO, VO,
TiO
2
, MnO
2
, WO
3
). BaTiO
3
nanoparticles are produced at about 400C in the following way.
Ba(OH)
2
+ TiO
2
BaTiO
3
+ H
2
O
Alkaline solution is used to increases the solubility.
5.7.4.SOLVOTHERMAL PROCESS
This process involves the use of a solvent under moderate to high pressure (1 to 10
4
atm) and
temperature (100C to 1000C).
This is the method used to prepare variety of nano-materials such as metals, ceramics, polymers,
semiconductors, metal oxides.
(A) ZnO nanorod is prepared by dissolving zinc acetate in 2-proponol at 50C. It is then cooled to
0C. Sodium hydroxide is added to precipitate ZnO growth. 1- dodecanethiol is used as decapping
agent.

5.11.Solvothermal method
(B) ZrO
2
nanorod is prepared by dissolving ZrO
2
Cl
2
in cyclohexane at 70C. It is then cooled to 0C.
NH
4
OH is added to precipitate ZrO
2
. The solution is then heated to 65C to allow the growth of
ZrO
2
in the form of a nanorod.
5.7.5.ELECTRODEPOSITION METHOD
This process consists of an electrochemical cell. This contains specially designed cathode and
anode. During electrolysis, nano structured materials are deposited at the cathode. A sheet of nano
structured copper can be fabricated by putting two electrodes in an electrolyte of copper sulphate and
applying a voltage between two electrodes. A layer of nano structured copper will be deposited on the
negative, titanium electrode. A sheet of copper with 2 nm thick can be made by this process. It has an
average grain size of 27nm.
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Figure.5.12.Electrodeposition method
The electrochemical oxidation of aluminium anode(positive electrode) in concentrated
phosphoric acid electrolyte using a platinum(cathode, negative electrode) working electrode, involves the
production of Al
3+
ions and the reduction of phosphate PO
3
4-
into phosphite PO
3
3-
ions plus co-generated
O
2-
ions. The oxide ions react with aluminum ions to form an over coating of aluminium trioxide on the
cathode.
The principle of electrodeposition is inducing chemical reactions in an aqueous electrolyte
solution with the help of applied voltage, e.g. this is the process of using electrical current to coat an
electrically conductive object with a relatively thin layer of metal. This method is relevant to deposition
of nanostructured materials include metal oxides and chalcogenides
Advantages
1. Nanofilms of Ni, Pt, Cu, Au having larger surface area can be prepared.
2. The films obtained are highly flat and uniform.
3. Even complex shapes can be coated.
5.7.6.CHEMICAL VAPOUR DEPOSITION (CVD) METHOD
This process involves the formation of nano materials from the gas phase at elevated
temperatures. The solid materials are converted into gas phase and deposited as nano materials.
The experimental arrangement for the production of carbon nanotubes (CNT) by this method is
shown in the figure.
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Figure.5.13.Chemical vapour deposition method(CVD)

Method
It consists of high temperature vacuum furnace. It has the provision to maintain the inert
atmosphere. The solid substrate, which contains catalysts like Fe, Co, Ni supported on MgO or
Al
2
O
3
is kept inside the furnace. The hydrocarbons such as methane, ethylene, acetylene and
nitrogen gas containers are connected to the furnace. Carbon atoms produced by the decomposition
of hydrocarbons at 1000C , condense on the cooler surface of the catalysts and form nanotubes. The
catalysts plays an important role in the formation of CNT.
Gallium arsenide semiconductor film is prepared by this method. Tri methyl gallium(Me
3
Ga) and
arsine (AsH
3
) mixture is heated above 1000C, compounds are decomposed and settled as a thin film
over hot substrate[SiO
2
] kept inside the tube. The methyl groups formed are removed by carrier gas
hydrogen.
Me
3
Ga(g)+ AsH
3
(g) + H
2
(g) GaAs (s) + CH
4
(g)
Advantages
1. The process is a continuous one. Hence, CNT is produced continuously
2. This is the low cost method.
3. High purity nano materials are obtained.
4. Both SWCNT and MWCNT can be produced.
5.7.7.LASER ABLATION METHOD
Laser ablation is a process of removing materials from a solid surface by irradiating it with a laser
beam.
Pulsed lasers are used to synthesis silver nano particles in the following way
Silver nitrate and a reducing agent are flowed through a blender like device. In the blender, there
is a solid disk which rotates in the solution. The solid disk is subjected to pulses from a laser beam
creating hot spots on the surface of the disk.
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Silver nitrate and the reducing agent react at these hot spots, resulting in the formation of silver
nanoparticles. This can be separated from the solution using a centrifuge.
The size of the silver nanoparticles is controlled by the energy of the laser and the rotation speed
of the disk.
This method is capable of a high rate of production of 2 to 3g/min.
ZrO
2
and SnO
2
nano films are obtained by this process.

Figure.5.14.Laser ablation method
ADVANTAGES
1. No solvent is used.
2. It is ecofriendly.
3. The running cost is low.
4. It is easy to operate even with robot.
5. Heating of the target is minimum.
6. The process is more gentle than other methods.
5.8.PROPERTIES OF NANOMATERIALS
The mechanical, electrical, thermal, chemical, magnetic, kinetic and optical properties of nano
materials change with the reduction in the particle size.
1) Mechanical properties
Nanomaterials have very high strength and super hardness. They are mostly free
from dislocations due to the presence of cluster of grains.
Youngs modulus of CNT is 10 times larger than that of steel.
The melting point of gold decreases from 1200 K to 800 K when the particles size
is reduces from 30 nm to 20 nm.
2) Electrical properties
Resistivity is the inverse of conductivity. In general, the resistivity of
19

nanomaterials is greater than that in polycrystalline materials. This is because, the electrons get scattered
at grain boundaries resulting in the increase of resistance.
The electrical properties of CNTs lie between metallic and semiconducting
materials. The high electrical conductivity is due to the minimum defects in its structure.
3) Thermal properties
Thermal conductivity of CNTs is very high. This is due to the vibration of
covalent bonds. This value is 10 times greater than that in metals.
4) Chemical properties
When the particle size is reduces from the bulk, the electronic bond in the metals
becomes narrow. It leads to the transformation of delocalized electronic states into more localized
molecular bonds. As a result, the ionization potential increases.
The large surface to volume ratio, the variations in geometry and electronic
structures have a strong effect on catalytic properties.
Magnetic properties
Nanomaterials of non magnetic solids also exhibit totally new types of magnetic
properties.
The magnetic moment of iron nanoparticles is more than 30% higher than that
of bulk. At smaller sizes, they become spontaneously magnetic.
5) Optical properties
The particle size of CdSe crystal from 1 to 50 nm is too small to scatter the visible
light. Hence, it becomes transparent.
Spectral shift of optical absorption, fluorescence properties and increased
quantum yield of semi conducting crystals are some optical properties of nanomaterials.
6) Kinetic properties
The inner tubes of multi walled carbon nanotubes (MWCNT) can slide without
any friction within the outer nanotubes. This leads to an atomically perfect rotational bearing.

5.9.APPLICATIONS OF NANOMATERIALS
The applications of nanomaterials are many. They are used in many fields and devices such as
electrical devices, memory devices, fuel cells, defense field, energy, optical devices, transport, medical
field. We shall discuss few of them.
1) Electrical and electronic devices
The nanomaterials are used for producing nano transistors, capacitors, noise filters,
display devices and quantum computing devices.
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The advantages of these devices are low power loss and small size.
Examples: ZnO, BaTiO
3
2) Memory devices
(i) Nano materials are used to produce very tiny permanent magnets of high energy product
value.