CORE 14 :

NANOCHEMISTRY
UNIT 1 : BASICS OF
NANOCHEMISTRY
INTODUCTION
ORGIN TO NANOCHEMISTRY:
1) The term Nnanochrmistry was derived from the Greek word “Nanos”
which means dwaf or exteremely small
2) It can be used as a prefix to mean a Billonth of that unit.
3) Any material having atleast one of its dimension between 1 to 100nm.
4) Example : Metal Rubber, Nanoparticle’s, Carbon Nanotubes, quamtum
dots.
Metal rubbers
* It is a conductive plastic polymer with metal ions.
Quantum dots
* Manmade Nano scale crystal that can transport electrons.
* Nano technology is coined by Noria Taniguchi in 1974.
How big is the Nano Meter ?
Nano is a unit of measure
Centimetre – one hundredth of a meter
Millimeter – one thousandth of a meter
Micrometer – one millionth of meter
Comparison between
macro/micro/nano scale
Macro scale MICRO SCALE Nano Scale
Average person Human Hair DNA = 2nm
Height 80,000nm,
180cm = 1.8B nm eye can see only upto cellulose Fibre = 3.5 to
Size of the apple 10,000 nm 100nm
8cm = 8M nm E.coll bacteria Hydrogen
Size of the Ant 2mm = 2000nm 0.1nm
5cm = 5M nm Mammalian cell
5mm to 100mm
Nano Science
It is defined as the science which deals with the ability to control and
manipulate matter at a scale ranging 1 to 100 Nano meter.
It deals with the scientific study of objects with sizes in the 1 to 100nm
range in atleast one dimension.
Nano Chemistry
It is a branch of Nano science it deals with study of synthesis,
characterization and application of Nano material
Nano Technology
The design characterization production and application of structure,
devices and systems by controlling shape and size on a Nano meter scale.
What is Nanotechonology
market ?
 31% Materials (Nano)

 17% Pharmaceuticals
 9% chemical manufacturing
 6% Aerospace
 9% others
Here are some nano particles used in
everyday life

• Sunscreen lotion
• cosmetics
• Deodrant
• Paint
• Air filters
• Purifiers
• Stain removers
Size relationship between
chemistry, Physics, Nanopaticles
Chemistry : Deals with atoms and molecules less than 1nm
Physics : Deals with solids od dimension is greater than 100nm. There exist a
gap between these two regimes and this is the regime of Nanoscale particle.
Nanosize (1-100nm)
* Size of atom/molecule is between 1 to 10nm
* Size of Nano particles 10 to 100nm.
* Size of bulk solid greater than 100nm
Size of typical biomolecules
Bio-Molecule size in
1. Gylscine 0.42nm
2. Chlorphyll 1.1nm
3. Insulin 2.2nm
4. Haemoglobin 7.0nm
What is a Nano material ?
The Material of at least 1 dimension between 1 to 100nm is called as
Nanomaterials.

What are the kinds of Nano Materialn?

Nano layer
Nano tube
Nano particles
Quantum dots
NANO LAYER :

Nano layer is a collective term used to denote a large group of extended two-dimensional and quasi-two-
dimensional Nano objects of different physical and chemical nature, from membranes of liposomes and cells to
graphene and flakes of layered double hydroxides.
Example: Titanium Dioxide, Graphene Oxide

NANO TUBE :
Nanotubes are a unique class of materials because of their hollow tubular nanostructure with diameters in the
nanometer regime
Nanotubes can have a single outer wall of carbon, or they can be made of multiple walls (cylinders inside other
cylinders of carbon)
Nanotubes have been constructed with length-to-diameter ratio of up to132,000,000:1.
Example: Carbon Nano Tube (CNT).
NANO PARTICLE :
A nanoparticle or ultrafine particle is usually defined as a particle of matter that is between1 and 100
nanometers (nm) in diameter.
Undetectable by the human eye, nanoparticles can exhibit significantly different physical and chemical
properties to their larger material counterparts
Example: Iron, Graphene, Silicon, Gold.

QUANTUM DOTS :
Quantum dots (QDs) are semiconductor particles a few nanometers in size, having optical and electronic
properties that differ from larger particles due to quantum mechanics.
They are a central topic in nanotechnology. When the quantum dots are illuminated by UV light, an electron in
the quantum dot can be excited to a state of higher energy.
In the case of a semiconducting quantum dot, this process corresponds to the transition of an electron from
the valence band to the conductance band.
The excited electron can drop back into the valence band releasing its energy by the emission of light.
 This light emission (photoluminescence) is illustrated in the figure on the right.

The color of that light depends on the energy difference between the
conductance band and the valence band.

When all the three dimensions are reduced, the electrons have no freedom to
move in any direction. Now, a zero dimensional (00)quantum dot structure is
obtained.

The motion of electron is confined in the x, y and z directions.

Hence, the electrons have no freedom to move in space (0D) Nano gold
particles have this type of quantum structure.

They are so small that about 3 million quantum dots can be fit within the width
of human thumb.
Quantum wires :
Quantum wires are extremely narrow structures where electron transport possible only in a very few
transverse modes (with energies less than the Fermi energy).

If two dimensions are reduced and one dimension remains large, the resulting structure is called o quantum
wire or quantum rod.

Quantum wires can be used as electron waveguides. Semiconductor quantum wires have been used to
make switchable high-speed lasers.

Here, the motion of electrons is confined in the x and y directions and the electrons are free to move in one
direction (1D).

Examples are metallic and semiconductor wires. General properties Materials when reduced to Nano size
display different properties.
GENERAL PROPERTIES :
Materials when reduced to Nano size display different properties. Scanned with Opaque substance become
transparent Eg: Copper
Inert materials became catalyst Eg.: Pt, gold.
When reduce the size insulator become conductor Eg. Silicon.
Nano materials are exceptionally strong hard, ductile.
Materials are wear-resistant, corrosion resistant and erosion resistant.(Wear-resistant)-not easily damage by
friction or over usage)
They are Chemically active
Nano material exhibit different color depends upon their size where gold is yellow colored But Nano particle
of gold is ruby red.
Nano materials when irradiate with UV-light emit visible light.
Melting point of Nano material is sower than that-of the bulk Reactivity of nm is more than that Of bulk
material
PROPERTIES OF NANOMATERIAL :

PHYSICAL PROPERTIES :

i)Color :

Light absorption in metals is due to excitation of conduction band electrons(Plasmon’s).

The Plasmon excitations and hence light absorption in bulk material occurs in the IR region.
However, when the size of the material is reduced to Nana scale, they are able to absorb light in the UV-
visible region
This blue shift causes depending on colour. For example, gold is yellow in colour
whereas Nano gold is ruby red in colour due to quantum effect.
ii) Melting point

The melting point changes when the physical size of the material approaches the Nanoscale

Melting-point depression is a term referring the phenomenon of reduction of the melting

point of a material with reduction of its size.

This phenomenon is very prominent in Nanoscale materials which melt at temperatures

hundreds of degrees lower than bulk materials.

However, as the dimension of a material

iii) Tensile strength :

Nanotubes nave high tensile strength (weight bearing capacity

This is due to high strength-to weight ratio. It is estimated that Nanotubes are about
100 times stronger than a high grade steel.

Spider silk is 10 times tougher than steel of the same mass. Factors responsible for
special properties of Nanomaterials

Two primary factors which cause Nanomaterials to behave significantly differently

from bulk materials are surface effects and quantum effects.
iv) Electrical conductivity:

According to Ohm's law, the conductance increases with decrease of resistance.

Metals are good conductors of electricity due to their low resistivity.

Nanoparticles show very little resistivity and hence they have high electrical conductivity

For example : doped fullerene with zero resistivity can act as superconductor.
Mechanical Properties :

Carbon Nanotubes are very strong. They have high tensile strength and stiffness. The tensile strength of CNT is
almost 20 times higher than of steel.

Magnetic Properties :
Nanomaterials exhibit magnetic properties that are different from those of bulk materials.

Decreasing the size of material to the Nanoscale can considerably improve the quality of magnet fabricated from it.
The magnetization increases significantly below grain size of 20 nm, hence, by decreasing the particle size of
material it is possible to improve the quality of magnets.

Ferromagnetism of bulk materials disappears and transfer to superparamagnetism in Nanomaterials due to the large
surface energy.

For example, iron oxide Nanoparticles were used to improve MRI images of cancer tumors.

The Nanoparticles were coated with a peptide which binds a cancer tumor. Once the Nanoparticles were attached to
cancer tumor, the magnetic property of Iron oxide Nanoparticles enhances the Images form the MRI scan.
 Quantum confinement is change of electronic and optical properties when the material sampled is of
sufficiently small size - typically 10 Nanometers or less.

The band gap increases as the size of the Nanostructure decrease. Specifically, the phenomenon results
from electrons and holes being squeezed into a dimension that approaches critical quantum measurement,
called the exaction Bohr radius.

Quantum confinement effects describe electrons in terms of energy even potential wells, valence bands,
conduction bands, and electron energy bandgaps The quantum confinement effect is observed when the size
of the particle is too small to be comparable to the wavelength of the electron.

Obviously, the confinement of an electron and hole in Nanocrystals significant depends on the material
properties, namely, on the Bohr radius.

These effects take place in bigger Nanocrystals and depend on the material properties, namely, on the
Bohr radius aß = 2.34 nm and a of about 10 nm, which would have Cd-related compounds such as CdTe,
CdžnTe, and CdTeSe .
There is a general rule that the bandgap of group I-VW semiconductors becomes narrower as the
constituent atoms become heavier.

In the case of Nanoparticles with diameters of ca. 2-10 nm, the bandgap is increased due to thee
quantum size effect compared with the bulk semiconductor, and it leads to various fluorescent colors
reflecting small differences in the particle size.It is one of the fundamental effects that appear in
Nanomaterials because free electron in that particular material get confined because of the size
reduction that occurs in Nanomaterials, i.e ("t is one of the size effect in quantum").

The size effect is going to play vital role in affecting the properties of theNanomaterial.10Scanned
with
The bulk solid generally has a polycrystalline structure and it has a grain structure, i.e Each region of this
material has a grain which is separated by grain boundaries.
Size of the bulk materials Ranges from a few mm o few cm Compare this with Nanomaterial.
Nanomaterial has size reduction, the materials appears like bulk materials but grain structure is V.
Small.

Thematerial is made up of not several grain but one or more grains. What happened when we
go down from bulk grains having many grains &Nanomaterials having only a few grains?

The free electron in bulk material has a large volume to move around i.e. the free electrons are
not confined whereas in the case of Nanomaterials having one or two grain, the electron has less
volume to move around & the free electron are confined. This is known as quantum confinement
effect.
SURFACE TO VOLUME RATIO
It may be called as increase in surface area to volume ratio Nano Materials have relatively
larger surface Area when compared to the same volume or mass of the material produced in a larger
form.
Let us consider a sphere of radius its surface area = 4x3.14xR x R its volume=
4/3x3.14 x R*RxR Surface area to volume ratio = 3/Thus when the radius of the
sphere decreases, its surface to volume ratio increases.

Let us consider one cubic volume shown in fig its surface area is 6m2When it is
divided into 8 pieces its surface area becomes 12m2When it is divided into 27
pieces its surface area becomes 18m
Conclusion:

When the given Volume is divided into smaller pieces it surface area increases

Hence a particle size decreases a greater proportion of atoms are at the surface compared to
those inside

Nanoparticles have much greater surface area per given volume compared with larger particles

It makes all the materials more chemically Active.