NANOCHEMISTRY

BOOKS ON NANOTEHNOLOGY
S.NO.

TITLE

AUTHOR

1.

Nanotechnology: Basic Science and Emerging

Technologies

Mick Wilson

2.

Nanotechnology (AIP-Press)

Gregory L. Timp

3.

Unleashing the Potentials of Nanotechnology

Torres Clivia M Sotomayor

4.

Nanocomposite Science and Technology

Braun Paul V

5.

Materials and Processes for Surface and

Interface Engineering

Pauleau Yves

6.

A Journey into the Nanoworld

Balzani Vincenzo

7.

Nanotechnology and Life

Jones Richard A L

8.

Nanosystems: Molecular Machinery,

Manufacuring and Computation

K. Eric Drexler

CONTENTS

Introduction
Principle
Methods of preparation
Properties
Techniques
Application Areas

Nanoscience
A discipline concerning with making,
manipulating and imaging materials having at
least one spatial dimension in the size range 1
100 nm

Nanotechnology
A device or machine, product or process based
upon individual or multiple integrated
nanoscale components

Nanochemistry

Utilization of synthetic chemistry to make

nanoscale building blocks of different:
Size and shape
Composition
Surface structure
Charge
Functionality.

Hierarchical Assembly
Feature of self-assembly, where primary building blocks
associate into more complex secondary structures that are
integrated into the next size level in the hierarchy. This
organizational scheme continues until the highest level in the
hierarchy is reached.
Characteristic of many self-assembling biological structures.

Few basic types

Nano powder/crystals
Nanotubes
Nanowires
Nanocomposites etc.

Nano powder/crystals
Crystals of nanometer dimensions.
Typical dimensions of 1 to 50 nanometers
(nm), intermediate in size between molecules
and bulk materials.
Exhibit intermediate properties.
Applications as:
o Biochemical tags
o As laser and optical components
o For the preparation of display devices
o For chemical catalysis.

Nanotubes

Hollow carbon tubes of nanometer dimensions.

Constitute a new form of carbon, configurationally
equivalent to a graphite sheet rolled into a hollow tube.
May be synthesized, with sizes ranging from a few microns
to a few nanometers and with thicknesses of many carbon
layers down to single-walled structures.
The unique structure of these nanotubes gives them
advantageous behavior relative to properties, such as
electrical and thermal conductivity, strength, stiffness and
toughness.

Nanowires
Very small rods of atoms.
Solid, dense structures, much like a
conventional wire.
Offer the potential for creating very
small IC components.

Nanocomposites

Comprise a large variety of systems composed of

dissimilar components that are mixed at the
nanometer scale.
Can be one-, two-, or three-dimensional; organic
or inorganic; crystalline or amorphous.
Behavior is dependent on not only the properties
of the components, but also morphology and
interactions between the individual components,
which can give rise to novel properties not
exhibited by the parent materials.
Size reduction from microcomposites to
nanocomposites yields an increase in surface

Methods of Preparation
By synthesis strategy
By nature of process
By medium of synthesis

1. By synthesis strategy
a. Bottom-Up Strategy:
By the agglomeration of atoms or particles.
b. Top-Down Strategy: (Attrition; like- erosion)
By breaking the larger particles to the nano size.
Generally done by high energy ball milling.

2. By nature of process
a. Physical methods:
Only the size of the particles can be reduced mechanically.
Physical properties will be changed.
No change in chemical properties.

Just the increase in chemical reactivity due to

increase in surface area.
b. Chemical methods:
Chemical properties get change according to the
route adapted.

chemical

3. By medium of synthesis
(i) Gas phase synthesis
(ii) Liquid phase synthesis
(iii)Solid phase synthesis

(i) Gas phase synthesis

Nano particles are formed as a result of
reactions among gaseous molecules, gas
molecule condensation or decomposition.

(ii) Liquid phase synthesis:

most widely used technique
Precipitation in homogeneous medium.
Routes:
a. Chemical precipitation
b. Hydro/solvo-thermal synthesis (Thermal hydrolysis)
c. Sol-gel synthesis
d. Micro-emulsion synthesis or synthesis in reverse
micelles

a. Chemical precipitation
Fast chemical reaction is required to obtain a high degree of
super-saturation of the product to favor homogeneous
nucleation.
Super-saturationis a
state of asolutionthat
contains more of the
dissolved material that
could be dissolved by
thesolventunder normal
circumstances.

b. Hydrothermal synthesis (Thermal

hydrolysis)
Aqueous solutions of metal salts or gels are
treated at elevated temperatures (100-300C) and
pressures above 1 atm.
Size and shape of nanoparticles can be controlled
by changing the conditions of the solutions:
pH
Concentration
Solvent and process conditions (temperature,
duration, etc.).

Hydrothermal synthesisis a technique of crystallizing substances from

high-temperature aqueous solutionsat high vapor pressures; also termed
"hydrothermal method". The term "hydrothermal" is ofgeologicorigin.
It is a method of synthesis ofsingle crystals.
Thecrystal growthis performed anautoclave.
At the hotter end the nutrient solute dissolves, while at the cooler end it is
deposited on a seed crystal, growing the desired crystal.
Possible advantages
The ability to create crystalline phases.
Materials which have a high vapor pressure near their melting points can
also be grown by the hydrothermal method.
The method is also particularly suitable for the growth of large good-quality
crystals while maintaining good control over their composition.
Disadvantages of the method include the need of expensive autoclaves,
and the impossibility of observing the crystal as it grows.

c. Sol- Gel synthesis

Process involves the alkoxide hydrolysis and a condensation reaction.
M(OR)x + yH-OH M(OR)x-y(OH)y + yROH
Partially hydrolysed species are then linked to form M-O-M bonds by
condensation via dehydration or dealcoholation.
-M-OH + HO-M- -M-O-M- + H2O
-M-OH + RO-M- -M-O-M- + ROH
So, the process involving hydrolysis, polymerization, nucleation and
growth condenses the molecular units together into small clusters
called sols, eventually leading to the formation of an insoluble three
dimensional network, the gel.

Thesol-gelprocess is a wet-chemical technique

starting from a chemicalsolution, which acts as the precursor for

an integrated network (orgel) of either discrete particles or
networkpolymers.

Typicalprecursorsare metalalkoxidesand metalchlorides, which

undergohydrolysisand polycondensation reactions to form either
a network "elastic solid" or colloidalsuspension

Formation of a metal oxide involves connecting the metal centers

with oxo (M-O-M) or hydroxo (M-OH-M) bridges to generate metaloxo or metal-hydroxo polymers in solution.

The sol evolves toward the formation of a gel-like diphasic system

containing

both

aliquidphase

andsolidphase

whose

morphologies range from discrete particles to continuous polymer

networks.

In the case of the colloid, a significant amount of fluid

may need to be removed initially for the gellikepropertiesto be recognized.

The most simple method is to allow time

forsedimentationto occur, and then pour off the remaining
liquid.Centrifugationcan also be used to accelerate the
process ofphase separation.

Removal of the remaining liquid (solvent) phase requires a

drying process.

The rate at which the solvent can be removed is ultimately

determined by the distribution ofporosityin the gel.

The sol-gel approach is a cheap and low-temperature

technique that allows for the fine control of the products

d. Micro-emulsion synthesis
Microemulsions: Thermodynamically stable, optically clear
dispersions of two immiscible liquids, such as water and oil.
They are formed, when a surfactant lowers the oil/water interfacial
tension allowing thermal motions to spontaneously disperse the two
immiscible phases.
Reverse micelles are molecular self assemblies from surfactants which
have a spherical shape with a hydrophillic core and a hydrophobic tail
on the sphere surface.
Most popular method to prepare Nano-sized inorganic particles as
oxides.

(iii) Solid phase synthesis

Nanoparticles are formed directly from solids or semisolids
(viscous liquids).
It belongs to top-down approach.
i) Mechanical Milling:
) Mechanical forces, involved in high energy ball milling, are used
to break bulk material down to bring it to nano-level.
ii) Mechano-chemical method:
) Involves the physical reduction in the material size as well as the
milling energy is used to initiate the chemical reaction between
the materials that are being milled.

Properties
Surface area: Large.
Reactivity: High due to the unsaturated bonds on their pristine surfaces.
Basic properties: Properties of materials change as:
- their size approaches the nanoscale.
- percentage of atoms at the surface of a material becomes significant.
Example- Gold nanoparticles melt at much lower temperatures (~300 C
for 2.5 nm size) than the gold slabs (1064C).
Optical properties: Often possess unexpected optical properties as they
are small enough to confine their electrons and produce quantum effects.
Example- Gold nanoparticles appear deep red to black in solution.

Techniques

Scanning tunneling microscope (STM)

Atomic force microscope (AFM)
Scanning electron microscopy (SEM)
Transmission electron microscopy (TEM)
X-ray diffraction (XRD), etc.

Application Areas

Medicine
Diagnosis
Drug delivery
Tissue engineering
Environment
Catalysis
Filtration
Energy
Computers
Aerospace
Refineries
Vehicle manufacturing
Food packaging
Optics
Textiles
Cosmetics