UNIT II NANOCHEMISTRY

Introduction
In recent years nanotechnology has become one of the most important and
exiting fields in physics, chemistry, biology and engineering and technology.
Nano means 10-9m.
A nanometer (nm) is one thousand millionth of a meter.
Atoms are extremely small and the diameter of a single atom varies from 0.1 to
0.5 nm depending on the type of the element.
For example, one carbon atom is approximately 0.15nm in diameter and a
water molecule is almost 0.3nm across.
A red blood cell is approximately 7,000 nm wide and human hair is 80,000 nm
wide.
Nanoscience
Nano science deals with the study of properties of materials at nano scales
where properties differ significantly than those at larger scale.
Nanotechnology
Nanotechnology deals with the design, characterization, production and
applications of nanostructures and nano devices and nano systems.
Nano materials
All materials are composed of grains. The visibility of grains depends on their
size.The materials processing grains size ranging from 1 to 100 nm, known as
nano materials.
NANOMATERIALS VS BULK MATERIALS
Nanomaterials are invisible to the naked eye. But the bulk materials, we can see
their particles. The difference between nanomaterials and bulk materials is that
nanomaterials have their size in 1-100 nm range at least in one dimension
whereas bulk materials have their size above 100 nm in all dimensions.
 Size dependant Properties of nanomaterials
When the material size of the object is reduced to nanoscale, then it exhibits
different properties than the same material in bulk form.
Opaque substances become transparent (copper);
inert materials become catalysts (platinum);
stable materials turn combustible (aluminum);
solids turn into liquids at room temperature (gold);
insulators become conductors (silicon).
The factors that differentiates the nanomaterials form bulk material is
1. Increase in surface area to volume ratio
2. Quantum confinement effect

Increase in surface area to volume ratio:

The ratio of surface area to volume is large for nano materials
Due to increase of surface area, more number of atoms will appear at the
surface of compared to those inside.
For example, a nano material of size 10nm has 20% of its atoms on its surface
and 3nm has 50% of its atoms.
This makes the nanomaterials more chemically reactive and affects the
properties of nano materials.

Quantum confinement effect

Nano materials are the intermediate state to solids and atoms. When the
material size is reduced to nanoscale, the movement of electrons are confined
and their energy levels have been changed.
This effect is called quantum confinement effect.
This affects the optical, electrical and magnetic properties of nanomaterials.
Size dependant Properties of Nanomaterials
Physical properties
Inter atomic distance:
When the material size is reduced to nanoscale, surface area to volume ratio
increases.
Due to increase of surface area, more number of atoms will appear at the
surface of compared to those inside.
So Inter atomic spacing decreases with size.
Thermal properties
Nano materials differ from bulk materials.
The melting Temperature and phase transition temperature are lower for
nano materials.
Pure gold melts at 1336 K but the melting point of nano gold decreases from
1200 K to 800K as the size of particle decreases form 300A 0 to 200A0.
Optical properties:
Different sized nano particles scatters different of light incident on it and
hence they appear with different colours.
The nano particles of gold appear as orange, purple, red or greenish in colour
depending on their grain size.
The bulk copper is opaque where as nanoparticle copper is transparent.
Magnetic properties:
The magnetic properties of nano materials are different from that of bulk
materials
For example, Fe,Co, and Ni are ferromagnetic in bulk but they exhibit super
paramagnetism.
Na, K, and Rh are paramagnetic in bulk but they exhibit ferro-magnetic.
Cr is anti ferromagnetic in bulk but they exhibit super paramagnetic.
Mechanical properties
The mechanical properties such as hardness, toughness, elastic modulus,
young’s modulus etc., of nano materials are different from that of bulk
materials.
In metals and alloys, the hardness and toughness are increased by reducing
the size of the nanoparticles.
In ceramics, ductility and super plasticity are increased on reducing grain size.
Hardness increases 4 to 6 times as one goes from bulk Cu to nanocrystalline
and it is 7 to 8 times for Ni.
Chemical properties
Nanocrystalline materials are strong, hard, erosion and corrosion resistant.
They are chemically active and have the following chemical properties.
1. In electrochemical reactions, the rate of increase in mass transport
increases as the particle size decreases.
2. The large Surface area to volume ratio, the variations in geometry and the
electronic structure of Nano particles have a strong effect on catalytic
properties.
3. Most of the metals do not absorb hydrogen. But the hydrogen absorption
increases with the decrease of cluster size in Ni, Pt and Pd metals.
 TYPES OF NANOMATERIALS
The classification of nanomaterials based on dimensions is as follows:
1. zerodimensional (0D),
2. one-dimensional (1D),
3. two-dimensional (2D) and
4. threedimensional (3D) nanomaterials
(i) Zero-dimensional nanomaterials: Here, all the three dimensions (x, y, z)
are at nanoscale, i.e., no dimensions are greater than 100 nm. It includes
nano particles, nanospheres and nanoclusters.
(ii) One-dimensional nanomaterials: Here, two dimensions (x, y) are at
nanoscale and the other is outside the nanoscale. It includes nanofibres,
nanotubes, nanorods, and nanowires.
(iii) Two-dimensional nanomaterials:
Here, one dimension (x) is at nanoscale and the other two are outside the
nanoscale. The 2D nanomaterials exhibit plate like shapes. It includes
nanofilms, nanolayers and nanocoatings with nanometre thickness.
(iv) Three-dimensional nanomaterials: These are the nanomaterials that are
not confined to the nanoscale in any dimension. These materials have three
arbitrary dimensions above 100 nm.
Definition, Properties & Applications of
1. NANOPARTICLES
A nanoparticle is a small particle that ranges between 1 to 100 nanometres in
size. Undetectable by the human eye, nanoparticles can exhibit significantly
different physical and chemical properties to their larger material
counterparts.

Most nanoparticles are made up of only a few hundred atoms.

The table below shows the size of nanoparticles compared to other

structures:

Particle Type Diameter Size Range

Atoms and small 0.1 nm
molecules
Nanoparticles 1 to 100 nm
Fine particles (also 100 to 2,500 nm
called particulate
matter - PM2.5)
Coarse particles 2500 to 10,000 nm
(PM10, or dust)
What are the types of nanoparticles?
Nanoparticles can be classified into different types according to the size,
morphology, physical and chemical properties. Some of them are carbon-based
nanoparticles, ceramic nanoparticles, metal nanoparticles, semiconductor
nanoparticles, polymeric nanoparticles and lipid-based nanoparticles.

Properties:

The material properties change as their size approaches the atomic scale. Due to
their very small size, nanoparticles have a very large surface area to volume ratio
when compared to bulk material, such as powders, plate and sheet.
So nanoparticles possess unexpected optical, physical and chemical properties.

For example, copper is considered a soft material but copper nanoparticles

smaller then 50nm are considered a very hard material, with drastically different
malleability and ductility performance when compared to bulk copper.

The change in size can also affect the melting characteristics;

Gold nanoparticles melt at much lower temperatures (300 °C for 2.5 nm size)
than bulk gold (1064 °C).

Moreover, absorption of solar radiation is much higher in materials composed of

nanoparticles than in thin films of continuous sheets of material.

Uses and Applications of Nanoparticles

The use of nano particles spans across a wide variety of industries, from
healthcare and cosmetics to environmental preservation and air purification.

1. The healthcare field, nano particles are used in drug delivery – to deliver
drugs directly to cancerous growths, as well as to deliver drugs to areas of
arteries that are damaged in order to fight cardiovascular disease.
2. In the cosmetics industry, mineral nanoparticles – such as titanium oxide –
are used in sunscreen. Zinc oxide particles have been found to have
superior UV blocking properties & is used in the preparation of sunscreen
lotions.
3. Nanomaterials have also been developed for use in the military. One
example is the use of mobile pigment nanoparticles being used to produce
a better form of camouflage, through injection of the particles into the
material of soldiers’ uniforms.
4. Absorption of solar radiation is much higher in materials composed of
nanoparticles and hence used to design photovoltaics (PV) and solar
thermal products .
 2.NANOCLUSTERS
The key difference between nano particles and nano clusters is that
nanoparticles are particles having dimensions between 1 to 100 nm, whereas
nanoclusters are collections of nano particles. Nano clusters are composed of up
to 100 atoms, but bigger ones containing 1000 or more are called nano particles.

These are mostly metal nano clusters. Typically, a nano cluster is about 2 nm &
the size may vary from 0.1 nm to 10 nm. They are the link between atoms and
nano particles.

Types of nanoclusters – 3 types

i. Vanderwalls nano clusters ii. Ionic nano clusters iii.Metal nano clusters

Nanoclusters tend to exhibit excellent mechanical, chemical, physical & magnetic

properties.

For example, vanadium and rhodium are paramagnetic in bulk but

become ferromagnetic in nanoclusters. Also, manganese is antiferromagnetic in
bulk but ferromagnetic in nanoclusters.

Gold nanocluster is an excellent example of a catalyst. While bulk gold is

chemically inert, it becomes highly reactive when scaled down to nanometer
scale

Applications:

Nanoclusters have many areas of application as they have unique optical,

electrical, magnetic and reactivity properties. Nanoclusters are used in bio
imaging or cellular labeling.

Nanoclusters are widely used as catalysts.

nanoclusters can be used in optical data storage that can be used for many years
without any loss of data
3. NANOWIRES

SILVER NANOWIRE SILICON NANOWIRE

Nanowires are just like normal electrical wires other than the fact that they
are extremely small. Like conventional wires, nanowires can be made from a
variety of conducting and semiconducting materials like copper, silver, gold,
iron, silicon, zinc oxide and germanium. Nanowires can also be made from
carbon nanotubes.

Nanowire Size: The diameter of nanowires are is between 3nm to 100

nanometers. (less than 100 nm ) but length to many meters . So Aspect Ratio
>1000 · 1000 times longer than its diameter

Types of nanowires:

i. Metallic nanowires – ( ex: Ni, Pt, Au)

ii. Semiconducting Nanowires - ( ex: Si, GaN)
iii. Insulating Nanowires – (ex: SiO2, TiO2)
iv. Molecular Nanowires – either organic or inorganic

Applications
Nanowires applications include:

1.Exceptionally small electronic circuits 2. Memory devices

3.Transistors 4. Advanced composite materials

5. Quantum devices 6. Biomolecular nanosensors

7.Optoelectronics 8. Field Emitters, p –n junctions & logic gates

 4. NANORODS
Nanowires and nanorods are very similar, and in most synthesis produced
together. The difference lies in the length to diameter ratio of the two. Nanorods
are thicker in comparison to nanowires. Nanorods have much shorter length
than nanowires and their diameters are greater than the wires

Nanowire : In Nanowires aspect ratio is around 1000.

Nanorod : In Nanorod aspect ratio can vary between 2 to 50.
Example, metallic nanorods, semiconductor nanorods, carbon nanorods, and
oxides nanorods,

Applications:

1.Gold nanorods can be used to deliver drug molecules to cells, tissue, or organs.

2. in cell imaging

3. In cancer therapy

4. In manufacturing micromechanical switches

5. In energy harvesting and light emitting devices

5. NANOTUBES

Nanotubes are tube like structure with diameter 1–100 nm and length few
nm. It may be either Inorganic – carbon , Si or Boron nitride nano tube or
Organic – DNA

Carbon Nano tubes:

Carbon Nanotubes are made by 'roling' single sheets of graphite

with honeycomb structures into very long, thin tubes that have a
stable, strong, and flexible structure.
Carbon nano tubes are tubular form of carbon in which graphite sheets are
rolled into a cylindrical form and their edges are joined .

Depending upon the way in which the graphite sheets are rolled, two types of
CNT are formed.

1. Single walled nano tubes (SWCNT)

2. Multi walled nano tubes. ( MWCNT)

SWCNT

The structure of a single walled carbon nanotube is like as the wrapping of a one-
atom-thick layer of graphite called graphene into a tube-like cylinder. A CNT is
considered as a single molecule with several hundreds oc Carbon atom

Three different structures of SWCNT are obtained by the way that the graphene
sheet is wrapped which is represented by a pair of indices (n,m).

The integers n and m denote the number of unit vectors along two directions in
the honeycomb crystal lattice of the carbon nanotubes.

If m = 0, the nanotubes are called zigzag nanotubes,

and if n = m, the nanotubes are called armchair nanotubes.

Otherwise, they are called chiral.

If the hexagons are parallel to the axis – arm chair CNT

If perpendicular – Zig Zag CNT

Diagonal – chiral

MWCNT

Multiwalled carbon nanotubes can be formed in two structural models:

Russian Doll model and Parchment model.

When a carbon nanotube contains another nanotube inside it and the outer
nanotube has a greater diameter than thinner nanotube, it is called the Russian
Doll model. On other hand, when a single graphene sheet is wrapped around
itself several times, the same as a rolled up scroll of paper, it is called the
Parchment model

Properties of carbon nanotubes

Apart from their electrical properties, CNTs also have unique thermal and
mechanical properties that make them useful for the development of new
materials:
their tensile strength can be 400 times that of steel;
they are very light-weight –
their density is one sixth of that of steel;
their thermal conductivity is higher;
they have a very high aspect ratio greater than 1000, i.e. in relation to their
length they are extremely thin;
just like graphite, they are highly chemically stable and resist virtually any
chemical impact.
APPLICATIONS OF CARBON NANOTUBES AND THEIR USES
CNTs are well-suited for virtually any application requiring high strength,
durability, electrical conductivity, thermal conductivity and lightweight
properties compared to conventional materials.
1. MATERIALS
Carbon nanotube enabled nanocomposites is a highly attractive alternative to
conventional composite materials
It has been estimated that advanced CNT composites could reduce the weight of
aircraft and spacecraft by up to 30%.
These composite materials already find use in sporting goods
Textiles, bullet-proof vests, automotive, aeronautics and space applications
 2. CATALYSIS
CNTs have been used as catalysts in many chemical processes, however,
controlling their catalytic activity is not easy.
3. TRANSISTORS
Semiconducting single-walled carbon nanotubes are used in high-performance,
ultra-scaled and thin-film transistors as well as for opto-electronic devices to
replace silicon electronics

4. SENSORS
CNTs are used as biosensors. It is used to detect many molecules present in the
blood.

5. NANO INKS
Ink formulations based on CNT dispersions are attractive for printed electronics
applications such as transparent electrodes, RFID tags, thin-film transistors, light-
emitting devices, and solar cells
6. ELECTRODES
Carbon nanotubes have been widely used as electrodes for chemical and
biological sensing applications and many other electrochemical studies.
7. DISPLAYS
Given their high electrical conductivity, and the incredible sharpness carbon
nanotubes are considered the most promising material for field emitters and a
practical example are CNTs as electron emitters for field emission displays (FED).
8. NANOMEDICINE AND BIOTECHNOLOGY
There is considerable interest in using CNTs for various biomedical applications.
The physical properties of CNTs, such as mechanical strength, electrical
conductivity, and optical properties, could be of great value for creating
advanced biomaterials.
Nitrogen-doped carbon nanotubes for instance have been developed for drug
delivery .