Nano Chemistry

(Unit V)
 NANOCHEMISTRY
Introduction
• Nano-denoting a factor of 10−9 (one billionth)

• Nano chemistry is a branch of nano science deals with the

chemical applications of nanomaterials in nanotechnology.
Nanochemistry involves the study of the synthesis and
characterisation of materials of nanoscale size.

• Nanochemistry is a relatively new branch of

chemistry concerned with the unique properties associated
with assemblies of atoms or molecules of nanoscale (~1-100
nm), so the size of nanoparticles lies somewhere between
individual atoms or molecules and larger assemblies of bulk
materials.
 NANOCHEMISTRY
• Nanotechnology is the characterization, production, design
and application of structures, devices and systems by
controlling size and shape at nanometer scale.
• Quantum Dot is a nanocrystal made of semiconductor
materials.
• Polymeric Nanoparticles: from polymers, as potential drug
delivery devices.
• Dendrimers: Polymeric nanoparticles constructed by
successive addition of layers of branching groups. Property
depends on functional groups.
• Nanomaterials: Having sizes in the range of 1 nm to
THE SCALE OF THINGS
THE SCALE OF THINGS
Micro science:

It is the sensible world of Sir Isaac Newton (and his

physical laws)

Nano science:

The rules of Quantum Mechanics => Mushy

electron waves take over

And Newtonian laws and assumptions are

frequently dead wrong!

The Science Changes! Microscience ≠ Nanoscience

 At Nanoscale:

1.Gravitational effects can be ignored

2.Quantum effects come into play

3.Surface effects dominate

4.Van der Waals forces become important

 Four important ways in which nanoscale
materials may differ from macroscale materials

– Gravitational forces become negligible and

electromagnetic forces dominate
– Quantum mechanics is the model used to
describe motion and energy instead of the
classical mechanics model
– Greater surface area to volume ratios
– Random molecular motion becomes more
important
 Negligible gravitational effects:

• Because the mass of nanoscale objects is so

small, gravity becomes negligible

 Gravitational force is a function of mass and distance

and is weak between (low-mass) nanosized particles
Dominance of Electromagnetic Forces

 Electromagnetic force is a function of

charge and distance is not affected by
mass, so it can be very strong even when
we have nanosized particles

 The electromagnetic force between two

protons is 1036 times stronger than the
gravitational force!
 Quantum Effects

• Classical mechanical models that we use to understand matter

at the macroscale break down for…
– The very small (nanoscale)
– The very fast (near the speed of light)
• Quantum mechanics better describes phenomena that
classical physics cannot, like…
– The colors of nanogold
– The probability (instead of certainty) of where an electron
will be found
 Surface Area to Volume Ratio Increases

• As surface area to volume ratio increases

– A greater amount of a substance comes in contact with
surrounding material

– This results in better catalysts, since a greater

proportion of the material is exposed for potential
reaction
 Random Molecular Motion is Significant

• Tiny particles (like dust) move about

randomly
– At the macroscale, we barely see
movement, or why it moves
– At the nanoscale, the particle is moving
wildly, batted about by smaller particles
 PROPERTIES OF NANOMATERIALS

The property of nanomaterials differ from atoms and bulk materials due
to
 Large fraction of surface atoms
 High surface energy
 Spatial confinement
 Reduced imperfections

1. Optical properties – silver and gold color varies with size

2. Diffusion properties – Sintering of nanomaterials occur at lower
temperature
3. Magnetic properties – silver and gold nano particles act as magnetic
particles
4. Catalytic properties – Excellent catalytic property than bulk
5. Electrical properties – size dependent – minimum defects in structure
6. Mechanical Properties – tough and hard- have wear and corrosion
resistance than bulk
 CLASSIFICATIONS OF NANOMATERIALS

Zero-dimensional nanomaterials include nanocluster materials and nano dispersions,

i.e. materials in which nanoparticles are isolated from each other.
One-dimensional nanomaterials are nanofibre(nano rod) and nanotubular materials
with fibre (rod, tube) length from 100 nm to tens of microns.
Two-dimensional nanomaterials are films (coatings) with nanometer thickness.
 SYNTHESIS OF NANOMATERIALS

16-01-2020 18
 SYNTHESIS OF NANOMATERIALS
Top down approach
Laser ablation
Chemical vapor deposition
– Electrochemical deposition
– Electro spinning

Bottom –up approach

Sol-gel method
Solvothermal method
– Vapor-liquid-solid (VLS) method
PREPARATION OF NANOPARTICLES – BOTTOM UP APPROACH
Sol-gel technique:
PREPARATION OF NANOPARTICLES – BOTTOM UP APPROACH
PREPARATION OF NANOPARTICLES – BOTTOM UP APPROACH

Sol-gel technique :
Step 1: Formation of different stable solutions of the alkoxide
or solvated metal precursor (Formation of sol).

Step 2: Gelation resulting from the formation of an oxide- or

alcohol- bridged network (the gel) by a polycondensation or
polyesterification reaction that results in a dramatic increase
in the viscocity of the solution.

Step 3: Aging of the gel (Syneresis), during which the

polycondensation reactions continue until the gel transforms
into a solid mass, accompanied by contraction of the gel
network and expulsion of solvent from gel pores.
PREPARATION OF NANOPARTICLES – BOTTOM UP APPROACH

Sol-gel technique :
Step 4: Drying of the gel, when water and other volatile
liquids are removed from the gel network. This process is
complicated due to fundamental changes in the structure of the
gel.

Step 5: Dehydration, during which surface- bound M-OH

groups are removed, there by stabilizing the gel against
rehydration. This is normally achieved by calcining the
monolith at temperatures up to 8000C.

Step 6: Densification and decomposition of the gels at high

temperatures (T>8000C). The pores of the gel network are
collapsed, and remaining organic species are volatilized.
PREPARATION OF NANOPARTICLES – BOTTOM UP APPROACH
Solvothermal method
• Solvothermal synthesis is a method for preparing a variety
of materials such as metals, semiconductors, ceramics, and
polymers.

• The process involves the use of a solvent under moderate to

high pressure (typically between 1 atm and 10,000 atm) and
temperature (typically between 100 °C and 1000 °C) that
facilitates the interaction of precursors during synthesis.

• If water is used as the solvent, the method is called

“hydrothermal synthesis.”
 PREPARATION OF NANOPARTICLES – BOTTOM UP APPROACH
Solvothermal method
Fe3O4 nanoflakes can be prepared by resolving FeCl2.4H2O,
N2H4.H2O and [C16mim]Cl (1-Hexadecyl-3-imidazolinium chloride).
The solution is heated to 180 0C to get nanoparticle.
 The process can be used to prepare many geometries
including thin films, bulk powders, single crystals, nanocrystals
especially quantum dots in many shapes including spheres, rods by
controlling the temperature, concentration and reaction time.

Precursor:
Titanium
n-butoxide

Precursor solution with

Example: TiO2 Nanocrystallites butyl alcohol in autoclave
 Zinc acetate dihydrate was dissolved in 2-propanol at 50 °C.
Subsequently, the solution was cooled to 0 °C and NaOH was added
to precipitate ZnO.
The solution was then heated to 65 °C to allow ZnO growth
for a period of time before a capping agent (1- dodecanethiol) was
injected into the suspension to arrest the growth.

The rod-shaped ZnO nanocrystals

TEM image of ZnO

PREPARATION OF NANOPARTICLES – BOTTOM UP APPROACH
Solvothermal method
Advantages:
• Simple and effective way for the synthesis of
nanostructured materials
• Low processing temperature
• High reproducibility
• Large scale production
• Ability to control the size and shape of the material
PREPARATION OF CARBO NANO TUBES – TOP DOWN APPROACH
Chemical Vapor Deposition
CVD is a thin film deposition method that uses
chemical reactions to deposit high quality layers of a
designated material on a suitably placed substrate.

This method involves decomposition of carbon source

such as vapours of methane, ethane, ethylene, acetylene,
xylene, their mixture, isobutane and ethanol in the presence of
catalyst at high temperatures and nucleation to form CNTs.

The process is often used in the semiconductor industry

to produce thin films. In typical CVD, the wafer (substrate) is
exposed to one or more volatile precursors, which react and/or
decompose on the substrate surface to produce the desired
deposit.
PREPARATION OF CARBO NANO TUBES – TOP DOWN APPROACH
• Precursors: Carbon sources (methane, ethane acetylene,
isobutane and ethanol)
• Catalyst: transition metals (Fe, Co, Ni)
• Temperature: 1100o C
• Chemical reactions involved in CVD:
• Thermal decomposition, reduction, oxidation, hydrolysis,
disproportionation, carburization, nitridization.
PREPARATION OF CARBO NANO TUBES – TOP DOWN APPROACH
Steps involved in Chemical Vapor Deposition
PREPARATION OF CARBO NANO TUBES – TOP DOWN APPROACH
Types of CVD
• Thermal (800 – 2000OC)
– High or low temperature
– Atmospheric or low pressure
– Cold or hot wall
– Closed or open
• Plasma (plasma assisted or plasma enhanced)
CVD (300 – 700O C)
• Laser (Thermal Laser or laser pyrolysis)
• Photo-laser CVD (Photolytic or Photo CVD)
PREPARATION OF CARBO NANO TUBES – TOP DOWN APPROACH
Applications of CVD
• Coatings – Coatings for a variety of applications such
as wear resistance, corrosion resistance, high temperature
protection, erosion protection and combinations
thereof.
• Semiconductors and related devices – Integrated
circuits, sensors and optoelectronic devices
• Optical Fibres – For telecommunications.
• Composites – to produce ceramic matrix composites
such as carbon - carbon, carbon-silicon carbide and
silicon carbide-silicon carbide composites.
• Powder production – Production of novel powders
and fibres • Catalysts • Nanomachines
PREPARATION OF CARBO NANO TUBES – TOP DOWN APPROACH
Laser ablation
Laser ablation is a technique where pulses of laser
radiation are used to evaporate the material from a target,
followed by the condensation on a substrate to produce thin
films.

It involves irradiation intense pulsed beam on the

graphite target containing small amount of nickel and cobalt.

An inert argon gas is allowed to pass into the quartz

tube reactor to sweep the evaporated carbon atoms to colder
copper collector. Then, they condense as high purity carbon
nanotubes
PREPARATION OF CARBO NANO TUBES – TOP DOWN APPROACH
Laser ablation

Laser Ablation Chamber Ablation Process

PREPARATION OF CARBO NANO TUBES – TOP DOWN APPROACH
Laser ablation
Factors influence ablation process:

Laser source
Structural and chemical composition of target
material
Chamber pressure
Flow and pressure of the gas
Temperature
Distance between the target and the substrate.
 Nano rods, Nanowires & Nanotubes
• In nanotechnology, nanorods are one morphology of nanoscale
objects. Each of their dimensions range from 1–100 nm. They
may be synthesized from metals or semiconducting materials.
Standard aspect ratios (length divided by width) are 3-5.

• A nanowire is a nanostructure, with the diameter of the order of a

nanometer (10−9 meters). It can also be defined as the ratio of the
length to width being greater than 1000.

• A nanotube is a nanometer-scale tube-like structure. A nanotube

is a kind of nanoparticle, and may be large enough to serve as
a pipe through which other nanoparticles can be channeled, or,
depending on the material, may be used as an electrical
conductor or an electrical insulator. (1-100 nm). Ratio is upto
100,000,000.
 PREPARATION OF NANOWIRES
Vapor–Liquid–Solid method
• The VLS method is useful for the growth of one-dimensional
structures, such as nanowires.

• This method involves absorption of the source material from

gaseous phase into a liquid droplet that act as catalyst.

• In VLS method a catalytic liquid alloy phase is used which can

rapidly adsorb (diffuse) a vapor to supersaturation levels, and
from which crystal growth can subsequently occur
from nucleated seeds at the liquid–solid interface.

• Silicon nano wires with diameters in the range of 4-5 nm and

lengths of several microns can be easily synthesized by VLS.
 PREPARATION OF NANOWIRES
Vapor–Liquid–Solid method

Synthesis of Silicon-Nanowires
 PREPARATION OF NANOWIRES
Electrochemical Deposition
Electro chemical deposition or electro deposition is
regarded as one of the most popular methods of pore
filling with conducing metals to obtain continuous
arrays of nanowires.

Anodic Aluminium Oxide (AAO) is used as

template for the nanowire fabrication.

The template is attached to the cathode, which is

subsequently brought into contact with the
deposition solution
 PREPARATION OF NANOWIRES
Electrochemical Deposition
 When a current or potential is applied, cations and
anions from the deposition solution diffuse towards the
pore mouth, then inside towards the bottom of pores
where electrochemical reactions of the species occur on
gold surface.

 Then NWs grow along the pores to the top. The length
of the NWs can be tuned by the time of
electrodeposition process.

 After pore filling, the pure arrays of NWs can be

obtained by dissolution of the template membrane in a
basic solution.
 PREPARATION OF NANOWIRES
Electrochemical Deposition
 PREPARATION OF NANOWIRES
Electrospinning
Electro spinning is a fiber production method which uses electric
force to draw charged threads of polymer solutions or polymer
melts up to fiber diameters in the order of some ten nanometers
Parameters which influence Electro spinning:
Molecular weight, molecular-weight distribution and architecture
(branched, linear etc.) of the polymer
Solution properties (viscosity, conductivity and surface tension)
Electric potential, flow rate and concentration
Distance between the capillary and collection screen
Ambient parameters (temperature, humidity and air velocity in
the chamber)
Motion and size of target screen (collector)
Needle gauge
 PREPARATION OF NANOWIRES
Electrospinning
Electro spinning, also known as electrostatic fibre
processing technique has been originally developed for the
generation of ultrathin polymer fibres with nanometre scale
diameters.

Electro spinning occurs when the electrical forces at the

surface of a polymer solution or melt overcome the surface
tension and cause electrically charged jet o ejected.

When jet dries or solidifies, an electrically charged fibre

remains. This charged fibre can be directed or accelerated by
electrical forces and then collected in sheets.
 PREPARATION OF NANOWIRES
Electrospinning
For the fabrication of nanoparticles, a small size is not the
only requirement.
Nanoparticles - characteristics:
(i) Monosized or with uniform size distribution
(ii) Identical shape or morphology,
(iii) Identical chemical composition and crystal structure
(iv)Individually dispersed or monodispersed,
(i.e. no agglomeration)
“Nanotechnology revolution” was catalyzed by the mid-1980s
discovery of carbon nanoclusters known as fullerenes (C60)
(Bucky Balls)

To date, the most common applications for fullerenes include MRI,

drug-delivery agents and light-activated antimicrobial Agents etc.

Based on type of bonding metallic, ionic, Vanderwaals and network

clusters.
• C60, containing
alternating six- and five
membered rings of sp2
hybridized carbon atoms.

• This is only one isomer

for C60, out of a
staggering total of 1,812
possible structures
A nanorod is typically a crystalline 1D nanostructure,
with an overall length comparable to its width.
(i.e., both dimensions are <100 nm).

As their name implies, another feature of nanorods is their

rigid sidewall structures.

The term “nanocrystal” is probably more appropriate for

these structures (or, more explicitly: “rod-like
nanocrystals”).

As such, nanorods are capable of stacking onto each other

to yield interesting 2D and 3D arrays
SEM pictures of ZnO nanorods
CARBON NANOTUBES: ALLOTROPE OF CARBON
CARBON NANOTUBES: ALLOTROPE OF CARBON
 CARBON NANOTUBES: ALLOTROPE OF CARBON

Even though the diameters of CNTs are orders of magnitude smaller

than a human hair, their tensile strength is 20 times greater than
steel – a property attributed to extremely strong sp2 bonding between
neighboring hexagonal units.

The electrical conductivity of SWNTs may vary from metallic to

semiconducting, depending on the way a graphene sheet is folded

For metallic SWNTs, the electrical conductance may exceed silver

or copper by three orders of magnitude.

Have high thermal stability.

CARBON NANOTUBES: ALLOTROPE OF CARBON
Graphite Sheet

Single Walled
Carbon Nano tube Multi Walled Carbon Nanotube
 CARBON NANOTUBES: ALLOTROPE OF CARBON
Single Walled Carbon Nanotube: Based on the hexagon lattice, three types single
wall nanotubes are visualized.

Arm Chair: The lines of hexagons are parallel to the axis of the nanotube.
Zig Zag: The lines of carbon bonds are down the centre
Chiral: This exhibits twist or spiral around the nanotubes
1. Nanotechnology Applications in Medicine

• Because of their small size, nanoscale devices can readily

interact with biomolecules on both the surface of cells and
inside of cells.
• By gaining access to so many areas of the body, they have the
potential to detect disease and the deliver treatment.

• Nanoparticles can deliver drugs directly to diseased

cells in your body.
• Nanomedicine is the medical use of molecular-
sized particles to deliver drugs, heat, light or
other substances to specific cells in the human
body.
• Quantum dot- that identify the location of cancer
cells in the body.
• Nano Particles - that deliver chemotherapy drugs
directly to cancer cells to minimize damage to healthy
cells.
• Nanoshells - that concentrate the heat from infrared
light to destroy cancer cells with minimal damage to
surrounding healthy cells.
• Nanotubes- used in broken bones to provide a
structure for new bone material to grow.
 2. Nano Computing Technology

Past
Shared computing thousands of
people sharing a mainframe computer

Present
Personal computing

Future
Ubiquitous computing thousands of computers sharing each
and everyone of us; computers embedded in walls, chairs, clothing,
light switches, cars….; characterized by the connection of things in
the world with computation.
3. Sunscreens and Cosmetics
• Nanosized titanium dioxide and zinc oxide are currently used in
some sunscreens, as they absorb and reflect ultraviolet (UV) rays.
• Nanosized iron oxide is present in some lipsticks as a pigment.
4. Fuel Cells
The potential use of nano-engineered membranes to intensify
catalytic processes could enable higher-efficiency, small-scale fuel
cells.
5. Displays
• Nanocrystalline zinc selenide, zinc sulphide, cadmium sulphide and
lead telluride are candidates for the next generation of light-emitting
phosphors.
• CNTs are being investigated for low voltage field-emission displays;
their strength, sharpness, conductivity and inertness make them
potentially very efficient and long-lasting emitters.
 6. Batteries

• With the growth in portable electronic equipment (mobile phones,

navigation devices, laptop computers, remote sensors), there is great
demand for lightweight, high-energy density batteries.

• Nanocrystalline materials are candidates for separator plates in

batteries because of their foam-like (aerogel) structure, which can
hold considerably more energy than conventional ones.

• Nickel–metal hydride batteries made of nanocrystalline nickel and

metal hydrides are envisioned to require less frequent recharging and
to last longer because of their large grain boundary (surface) area.
7. Catalysts
In general, nanoparticles have a high surface area, and hence provide
higher catalytic activity.
8. Magnetic Nano Materials applications
• It has been shown that magnets made of nanocrystalline yttrium–
samarium–cobalt grains possess unusual magnetic properties due
to their extremely large grain interface area (high coercivity can be
obtained because magnetization flips cannot easily propagate past
the grain boundaries).

• This could lead to applications in motors, analytical instruments

like magnetic resonance imaging (MRI), used widely in hospitals,
and microsensors.

• Nanoscale-fabricated magnetic materials also have applications in

data storage.

• Devices such as computer hard disks storage capacity is increased

with Magnetic Nano materials
 9. Medical Implantation
• Unfortunately, in some cases, the biomedical metal alloys may wear
out within the lifetime of the patient. But Nano materials increases
the life time of the implant materials.
.
• Nanocrystalline zirconium oxide (zirconia) is hard, wear resistant,
bio-corrosion resistant and bio-compatible.

• It therefore presents an attractive alternative material for implants.

• Nanocrystalline silicon carbide is a candidate material for artificial

heart valves primarily because of its low weight, high strength and
inertness.
 10. Water purification
•Nano-engineered membranes could potentially lead to more energy-
efficient water purification processes, notably in desalination process.

•Recently, a research study showed that graphene-based water filter

removes more than 99% of natural organic matter
11. Military Battle Suits

• Enhanced nanomaterials form the basis of a state-of- the-art

‘battle suit’ that is being developed.

• A short-term development is likely to be energy-absorbing

materials that will withstand blast waves;

• longer-term are those that incorporate sensors to detect or

respond to chemical and biological weapons (for example,
responsive nanopores that ‘close’ upon detection of a
biological agent).
Assessment Question paper pattern

Part A – 5 x 2 = 10
Part B – 1 x 8 = 08 (Compulsory question)
– 2 x 16 = 32 (Either or)
----------
Total – =50
----------
I Assessment Portion
Polymer Chemistry and Nano Chemistry