Applications of Nanomaterials

Outline
❑ Introduction to
• Nanochemistry/Nanoscience/Nanomaterials

❑ Nanotechnology applications

❑ Synthesis, properties & potential applications of

carbon nanotubes, fullerenes and graphene, nano-
catalysis.

❑ Material self assembly, Molecular vs material self-

assembly

❑ Synthesis-top down and bottom up.

 What is NANOCHEMISTRY?
•Nanochemistry is a branch of nanoscience, is the study of
the chemical behaviors of very small particles of a substance

•Nanochemistry is an emerging new field of chemistry

Nanochemistry is the study of chemistry at the nano-scale.

OR

Nanochemistry is the combination of chemistry and

nanoscience.

Nanochemistry is associated with synthesis of nanomaterials

whose properties are dependent on size, surface, shape and
defects.
Nano chemistry is the study of atom by atom or
extremely small things in chemistry, physics, biology,
materials science, and engineering and its applications.

Nano chemistry is an advance area of chemistry for the

study of nanoparticles and their compounds reactions
and the production.

Nanochemistry also covers medicine, computing,

scientific exploration, and electronics, where
nanochemistry offers the promise of building objects.
 Materials
Atoms/Molecules

A Few
Atoms/Molecules

Nanomaterials

Micromaterials

Macromaterials

Bulk materials

Comparison of the sizes of nanomaterials with those of other common materials.

Int. J. Mol. Sci. 2014, 15, 7158-7182
 Nano-scale: how small is 1 nanometer?

1 mm = 10-3 m
1m = 10-6 m
1nm = 10-9 m
0.1 nm = 1 Ǻ = 10-10 m

Comparison between Nanomaterials and Bulk Materials

 Why Nanomaterials are so important?
•Nanoparticles have a high surface to volume
ratio which has a dramatic effect on their properties
compared to bulky forms of the same material.

The surface area of a cube = 6a2 where a is the length of the side of each edge of
the cube.
The formula of volume of the cube is given by: Volume = a3
 Why Nanomaterials are so important?
•Nanoparticles have a very high surface to volume
ratio and this gives them special properties different
from the bulk material

e.g.
• This difference in surface area / volume ratio for
the particles of the material give nanoparticles
extra chemical reactivity compared to the bulk
material,

• less of a material like a catalyst is needed in a

chemical process, so catalysts based on
nanoparticles are more efficient than those based
on bulk material catalysts.
What happens when size is reduced from bulk to nano?
Properties of the material changes

• band gap increases

Colour change of Au nanoparticles with size

•Pieces of gold are, fairly obviously, gold-coloured, but gold

nanoparticles are deep red or even black when mixed with
water.
 Wavelengths of Spectral Colors
10
http://csep10.phys.utk.edu/astr162/lect/light/spectrum.html
 Optical Properties Are Directly Dependent on Size
EXAMPLE: Gold and silver nanoparticles
Cut to 1000nm the color would be golden color.
Cut to 700nm the color would be red.
Cut to 600nm the color would be orange.
The color changes because each color has a specific
wavelength.

11
http://www.nanohub.org/resource_files/2006/02/01023/2006.02.13-ratner-nano201.pdf
 Nanomaterials
Why are we interested in nanomaterials?
Nanomaterials are of great interest because they have a lot of potential to
create new and innovative products across many areas.

Highly Symmetric Gold Nanostars

SEM and TEM images of Au nanostars synthesized with

different amines: (a,b) methylamine, (c,d) ethylamine, (e,f)
octylamine. Scale bars: (a,c,e) 200 nm; (b,d,f) 50 nm.

Note: Physicochemical properties vary with size and shape

Chem. Soc. Rev., 2013,42, 2679-2724

J. Am. Chem. Soc. 2015, 137, 33, 10460–10463
Physical properties of materials

• Thermal conductivity

• Electrical conductivity (resistivity)

• Surface area

• Porosity

• Thermal expansion

• Corrosion resistance

• Density

• Melting point

• Visibility
NANOSCIENCE & NANOTECHNOLOGYAPPLICATIONS

Nanoscience and nanotechnology are the study and application

of extremely small things and can be used in fields of
chemistry, biology, physics, materials science, and
engineering.
❑ Medicine
❑ Catalysis
❑ Environmental technologies
❑ In electronics and related fields (Computers, Mobiles etc.)
❑ In Mechanics
❑ In Surface nanoengineering
❑ Miscellaneous uses
• Energy (energy production & storage)
 NANOTECHNOLOGY IN MEDICINE
➢ Provide new options for drug delivery and drug therapies.

➢ Enable drugs to be delivered to precisely the right location

in the body and release drug doses on a predetermined
schedule for optimal treatment.

➢ Attach the drug to a nanosized carrier.

➢ They become localized at the disease site, i.e cancer

tumour.

➢ Then they release medicine that kills the tumour.

➢ Current treatment is through radiotherapy or

chemotherapy.

➢ Nanobots can clear the blockage in arteries.

 ➢ Gold nanoparticles can be used to detect early-stage
Alzheimer’s disease.

➢ We can prevent blindness by treating glaucoma(A group of eye

conditions that can cause blindness) using nanoparticle eye drops.

➢ Nanotechnology vacancies for diseases such as

hepatitis(An inflammation of the liver) one injection cost may be low.

➢ To facilitate bone regeneration in the treatment of

osteoporosis(A condition in which bones become weak and brittle).

Alzheimer's disease is a progressive neurologic disorder that causes the brain to shrink (atrophy) and brain cells to die.
It is a progressive disease that destroys memory and other important mental functions.
❑ Nanotechnology has been used in the early diagnosis of
atherosclerosis (is the buildup of fats, cholesterol and other
substances in and on your artery walls). Researchers have
developed an imaging technology to measure the amount of an
antibody- nanoparticle complex that accumulates specifically in
plaque. Clinical scientists are able to monitor the development
of plaque as well as its disappearance following treatment (see
image).

❑ Picture of atherosclerotic placque in a mouse artery. Placque

accumulation is shown in this image by the increasing intensity
of color.
NANOTECHNOLOGY IN CATALYSIS
The nanoparticles have large surface area and hence provide higher
catalytic activity. This property finds use in catalysis by precious
metals such as Pd, Pt and Rh.

These metals are widely used as catalysts but they are very expensive.
The nanosize of these catalysts increases the reactive surface area,
making them extremely active and thereby economising their use.

The active metal nanoparticles are supported on powdered material in

the form of beads, platelets, etc.

Similarly, although bulk aluminium is used for making utensils,

nanoaluminium becomes so reactive that it finds its use as a solid fuel
in rocket propulsion. It supplies the required thrust to propel the
rocket in space.
IN ENVIRONMENTAL TECHNOLOGIES
Nanoparticles are being widely used to control environmental pollution.
Nanoparticles on powder supports or on tubular monoliths form a
catalytic system used widely in the removal of pollutants such as
oxidation of volatile organic compounds (VOCs) in chimneys.

Oxidation of flue gases in the catalytic converters of petrol-burning

internal combustion engines where CO is oxidised to CO2 (in the presence
of Pt catalyst). NOX is removed by reducing it to N2 in the presence of
CO (catalyst Rh), and hydrocarbons are oxidised to CO2 and H2O using Pd
catalyst.

Similarly, cerium oxide nanoparticles are used in diesel engines for

pollution control.They trap the carbon particles (soot) formed because of
incomplete combustion, hence are used in filters.

Monoliths
IN ENVIRONMENTAL TECHNOLOGIES

What is a Catalytic Converter?

A catalytic converter is a sort of chemical filter made of rare metals. It’s

part of your car’s exhaust system. It keeps harmful pollutants from entering
the atmosphere by passing hot exhaust gases through a honeycomb of rare
metals like palladium and rhodium. Chemical reactions convert some of the
harmful gases into harmless gases.

A catalytic converter lasts about 10 years, depending on how much you drive
your car. A small one is about the size of a loaf of bread, while a large one can
be three times that. They’re mounted on the bottom of cars, easily found on
the exhaust system, which is part of the problem.
IN ELECTRONICS AND RELATED FIELDS

Nanomaterials are widely used in electronic circuits used

in television, radio, telephone, automobiles, aeronautics, etc. Use of
nanomaterials helps in reducing the size of these gadgets.

The properties of particles of nanodimensions are used to develop

sensors whose functional units are nanoentities, although the material
itself is not nano in dimension. The high surfaceto-volume ratio of
nanomaterials, their optical, electrical and physical properties help them
initiate response to the minute change in the concentration of the
species to be detected.

Solid-state techniques can also be used to create devices known as

nanoelectromechanical system or NEMS that are related to
microelectromechanical system or MEMS.

• Batteries Nickel metal hydride batteries made of nanocrystalline

nickel and nickel hydrides last longer and require less frequent charging
❑ Nanotechnologies for Flexible Electronics. Nanomaterials
are playing a vital role in the development of flexible
electronics. Only by manipulating the nanoscale structure
of materials can we create components with the
necessary electronic properties which can also be made
flexible.
IN MECHANICS
Nanoparticles are used to improve the performance of tyres and
improve mechanical properties of ceramics and alloys. The
common uses of nanoparticles to improve the mechanical
properties are as follows:

• Tyre The properties of a good tyre include reduced roll

resistance that decreases the petrol consumption, good road
holding capacity especially when the road is wet or covered with
snow and it should have resistance to wear to improve its lifetime.

Nanoparticles of precipitated silica are added to tyres to improve

their resistance to rupture, increase hardness and make them
more durable. These highly dispersible silica (HDS) improve their
road holding capacity, reduce roll resistance and increase their
resistance to wear.

• Addition of nano-structured particles to metal–ceramic

composites (cermets) improve their hardness, tensile strength
and elastic modulus-bonding strength.
• Alumina nanofibers and carbon nanotubes added to polymers
make them stiffer, prevent them from deformation, increase
stability to heating effects, make them more waterresistant and
improve their load-bearing strength.

• Polymers such as polylactic acid (PLA) are used for packing

food and medicines, although biodegradable they lack mechanical
strength. Addition of clay improves mechanical strength without
affecting its biodegradability.

• Nanoporous solids act as shock absorbers and molecular

springs. This is accomplished by intruding a lyophobic liquid (non-
wetting liquid) inside the porous solid. They find application in
car bumpers, suspension for vehicles, devicing systems to
protect buildings from seismic vibrations and various other
devices. The lyophobic liquid is intruded and extruded on the
application and release of pressure
IN SURFACE NANOENGINEERING

Nanoparticles are used for making self-cleaning surfaces. Water

from the damp air condenses on the glass surface, making it
difficult to see through it. Coating these glass surfaces with
TiO2 nanoparticles make the glass hydrophilic, rather than
hydrophobic so that the condensed droplets spread as a
continuous layer and prevent the distortion of visual image.
Similarly, deposition of TiO2 nanoparticles on ceramic and
polymer surfaces leads to self-cleaning surfaces.
MISCELLANEOUS USES
Nanoscale magnetic materials are used for data storage
devices such as computer hard discs. The use of
nanoparticles improves the storage capacity of the disc.

Nanotechnology in Memory and Storage.

❑ 2 gigabyte hard drive weighs about 70 pounds (31.7 KG). It was
first used in the 1980s. Its cost at that time ranged from $80,000
to $140,000.

❑ 2 GB in 1980s $80,000 2 GB in 1990s $200 2 GB in 2010 $5.

❑ Current research shows that by using nanotechnology,

1 000 GB of memory can fit on the head of this pin. 1000 GB is 1
Terabyte.
 Materials: Three major allotropes of carbon
2004
1985 one-dimension two-dimension
zero-dimension Carbon nanotube Graphene
Fullerene 1991

Bulk
C60 [0D, molecules]
(Buckminsterfullere
ne or bukyball)

Amorphous carbon
Diamond: transparent, insulator

C70 Fullerene

Graphite: Black, conductor or semimetal

C540 Fullerene
 Three major allotropes of carbon
Carbon nanotube
1985 Fullerene 1991 (CNT) 2004 Graphene

Sumio Iijima and Donald S Bethune The Nobel Prize in

Robert Curl,Richard Physics 2010 was
Smalley and Harry Kroto, awarded jointly to
shared the 1996 Nobel Andre Geim and
Prize in Chemistry for Konstantin Novoselov
their discovery of
fullerenes. Nobel Prize
 Activated carbon powder
Granular activated carbon

Charcoal Toothpaste
charcoal-based skincare products
Synthesis, properties & potential applications
of Graphene
 Graphene
What they are, how they are made, what they are used for
Graphene is an allotrope of carbon that exists as a two-dimensional planar
sheet. Graphene is as a single atomic graphite layer.

Graphene is a material composed of carbon atoms grouping that are

hexagonally positioned. This arrangement results in monolayers of an atom
thick.

Graphene

This material is part of one of the most abundant substances in nature, graphite
(graphite can be found, for example, in the mines of our pencils). One millimeter
of graphite contains three million layers of graphene.
Synthesis of Graphene

There are 3 main ways to synthesize graphene, they are:

❑ Chemical Vapor Deposition

❑ Chemical or Plasma Exfoliation from natural Graphite

❑ Mechanical cleavage from natural Graphite

Scanning Electron Microscope (SEM) Images of Graphene

SEM images of Graphene

 PROPERTIES OF GRAPHENE
The most outstanding properties of graphene are:
•High thermal conductivity
•High electrical conductivity
•High elasticity and flexibility
•High hardness
•High resistance. Graphene is approximately 200 times
stronger than steel, similar to diamond resistance, but much
lighter.
•Ionizing radiation is not affected
•Able to generate electricity by exposure to sunlight
•Transparent material
•High density which doesn’t let Helium atoms pass, but it does
allow the passage of water, which evaporates at the same
speed as if it were in an open container.
•Antibacterial effect. Bacteria are not able to grow in it.
•Low Joule effect, heating when conducting electrons.
•Low electricity consumption compared to other compounds
 APPLICATIONS OF GRAPHENE
Due to the great properties mentioned above, graphene has
applicability in numerous sectors, the most known are shown in the
following figure.

❑ In the field of electronics, graphene is used, for example,

in the manufacture of
• microchips,
• transistors,

❑ Development of conductive inks that allow the circuits printing.

❑ Graphene can enhance the use of renewable energy, such as solar

energy.

❑ By introducing this material into the solar panels it will be possible to

increase its efficiency and produce more energy.

❑ In the automotive sector, the use of graphene in batteries will

increase its autonomy and reduce charging times, thus improving the
performance of electric cars.
Synthesis, properties & potential applications
of carbon nanotubes,
 What are carbon nanotubes?
Carbon nanotubes (CNTs) are cylindrical molecules that
consist of rolled-up sheets of single-layer carbon atoms
(graphene). They can be single-walled (SWCNT) with a
diameter of less than 1 nanometer (nm) or multi-walled
(MWCNT), consisting of several concentrically interlinked
nanotubes, with diameters reaching more than 100 nm. Their
length can reach several micrometers or even millimeters.

Graphene

The purple structure is a human hair fragment,

with a diameter of about 80 to 100 thousand
nanometers and in the background is a network of
single-walled carbon nanotubes. (Image: Jirka
Cech)
https://www.nanowerk.com/nanotechnology/introduction/introduction_to_nanotechnology_22.php
Structure of SWCNT
CNTs are chemically bonded with sp2 bonds, an extremely
strong form of molecular interaction like their building block
graphene.

This feature combined with carbon nanotubes' natural

inclination to rope together via van der Waals forces, provide
the opportunity to develop ultra-high strength, low-weight
materials that possess highly conductive electrical and
thermal properties. This makes them highly attractive for
numerous applications.

Schematic of how graphene could roll up to

form a carbon nanotube.
Synthesis of Carbon nanotubes
Carbon nanotubes are produced in the following manners:
(i) Evaporating graphite rods in a dynamic atmosphere of
helium.
(ii) Laser evaporation of graphite produced SWNT. A
mixture of graphite is heated with Fe and Ni catalysts at
1200 °C and the material is irradiated with laser. It yields
50%–70% CNT.
(iii) SWNTs and MWNTs can be synthesised by chemical
vapor deposition. An organometallic precursor and carbon-
containing feed gas are mixed and pyrolysed in a quartz tube.
The nanotubes thus formed are collected from the cooler
end.
(iv) Both MWNTs and SWNTs are formed with carbonaceous
matter and can be separated by heat treatment. The
amorphous carbon material is burnt off by heating the soot
at 750 °C for half an hour; the product thus obtained is a
mixture of nanotubes.
Scanning Electron Microscope (SEM) Images of Graphene and CNTS

SEM images of
Graphene

SEM images of
Carbon nanotubes
Graphene Transmission Electron Microscope Images of Graphene and Carbon nanotubes

TEM images of
Graphene

Carbon nanotubes

SWCNT TEM images of MWCNT

Carbon nanotubes
 PROPERTIES OF CARBON NANOTUBES
• They have unique electronic and mechanical properties.

• They are 100,000 times thinner than the human hair.

• They combine rigidly and flexibly and can be hundreds of times stronger
than steel, but six times lighter.

• They possess very high tensile strength and stiffness.

• Their compression strength is in the range of 100–150 GPa.

• They can withstand large strains and show considerable elasticity and
capability of atomic rearrangement.

• Their electronic properties depend on the manner in which they are

closed at the ends. The electronic properties are greatly influenced by the
symmetry and helicity or chirality with respect to the tube axis. This
alignment, however, does not affect the mechanical properties of CNTS.

• They posses high conductivity, chemical specificity and inertness.

Table 1 Mechanical properties of different materials for
comparison of carbon nanotubes

Carbon nanotubes are supermaterials that can be stronger than steel and
more conductive than copper

Nanoscale Research Letters (2015) 10:358

Table: Transport properties of conductive materials

Carbon nanotubes are supermaterials that can be stronger than steel and
more conductive than copper
APPLICATIONS OF CARBON NANOTUBES
CNTs have a wide range of potential applications because of their exceptional
material properties such as high electrical and thermal conductivity, strength,
stiffness and toughness. They find their use in the manufacture of reinforced
composites, sensors, nanoelectronics and display devices.
Some of their applications are as follows:
(i) SWCNT is strong and stiff with strength hundreds of times stronger than steel
and are much lighter; hence, they are used for making light but strong composite
materials. SWNTs are the strongest known material. Owing to their strength, they
are widely used in manufacturing reinforced plastics, car and aeroplane parts and
in sports goods.
(ii) MWCNTs have good heat and electrical conductivity and they find use in
chemical sensors, conducting paints, hydrogen storage and in the manufacture of
composite materials.
(iii) SWNTs find use in solar panels because of their tendency to absorb
ultraviolet/visible and near infrared light.
(iv) SWNTs are used for hydrogen storage owing to their capillary effects.
(v) Electrically conducting CNT films are used in LCDs, touch screens and
photovoltaic devices. These films are also used for displays in computers, cell
phones, ATMs, etc.
(vi) MWNTs generate strong electrical field and are used for electric motor
brushes.
(vii) MWNTs are used in lithium ion batteries and silicon-coated carbon nanotubes
are used as anodes for Li- ion batteries.
 Fullerene
Fullerene is nothing but an allotrope of carbon wherein its
molecules consist of carbon atoms that are connected by single
and double bonds. This results in the formation of a closed or
partially closed cage-like structure (a mesh consisting of fused
rings) that further contain several atoms. The fullerene
molecule in this form can either have a hollow sphere, be an
ellipsoid, tube, or it can also have many other different shapes
and sizes.
 Structure of Fullerene
Fullerenes in their natural form tend to be highly symmetrical. Their
structure is quite similar to that of graphite and is made up of a sheet
of connected hexagonal rings (cage structure). However, they have
pentagonal and sometimes heptagonal rings which do not allow the sheet
to become planar. They are often referred to as buckyballs and
buckytubes depending on their shape. Cylindrical fullerenes are referred
to as nanotubes.

Model of the C60 fullerene

(buckminsterfullerene).

In any case, there is an infinite number of fullerenes that can exist. Fullerenes can be
C60, C70, C80, and C90 existing in various forms. This depends largely on the number
of carbon atoms present in the molecule. Nonetheless, their structure is primarily
based on pentagonal and hexagonal rings that are constructed as per the rules for
making icosahedra.
Synthesis of Fullerenes

Fullerenes are mainly synthesized by

arc discharge and laser ablation technique using graphite
as a source
Physical Properties of Fullerene
•Its behaviour and structure depend on the temperature. As
the temperature is increased fullerene gets converted into
the C70.
•Fullerene structure can change under different pressures.
•Fullerene has an ionization enthalpy of 7.61 electron volts.
•Its electron affinity is 2.6 to 2.8 electrons volts.
Chemical Properties of Fullerene
•Fullerenes are stable, but not totally unreactive.
•In chemical reactions, fullerene can act as an electrophile.
•It acts as an electron-accepting group and is characterized
as an oxidizing agent.
•Fullerenes when doped or crystallized with alkali or alkaline
earth metals it showcases superconductivity properties.
•Fullerene is ferromagnetic.
•Some fullerenes are inherently chiral.
•It is soluble in organic solvents such as toluene,
chlorobenzene, and 1,2,3-trichloropropane.
Applications of Fullerene
Buckyballs and carbon nanotubes have been used as building
blocks for a great variety of derivatives and larger
structures.
•Fullerenes are used in the medical field as light-activated
antimicrobial agents.
•It is also used in several biomedical applications including the
design of high-performance MRI contrast agents, X-ray
imaging contrast agents, photodynamic therapy and drug and
gene delivery.
•Buckminsterfullerene is used in drug delivery systems, in
lubricants and as a catalyst.
•It is also used as a conductor.
•Some types of fullerene can be used as an absorbent for
gases.
•It is used in making cosmetic products.
•C60 based films are used for photovoltaic applications.
•Fullerenes are used in making carbon nanotubes based fabrics
and fibres.
Nanomaterials Synthesis
 Self-assembly
Self-assembly is defined as the spontaneous association of numerous
individual units of material into well organized and well defined
structures without external direction. (OR)
Self-assembly is a process in which a disordered system of pre-existing
components forms an organized structure or pattern as a consequence
of specific, local interactions among the components themselves, without
external direction.

When the constitutive components are

molecules, the process is termed
molecular self-assembly.
When the constitutive components are
materials, the process is termed
materials self-assembly.
 Nanomaterials Synthesis
Bottom-up approach Top-down approach

Top-down approach involves the

Bottom-up, or self-assembly,
breaking down of the bulk
approaches to nanofabrication use
material into nanosized
chemical or physical forces
structures or particles.
operating at the nanoscale to
assemble basic units into larger
structures.
In general, bottom-up approach is meant by synthesis of nanoparticles by means of chemical
reactions among the atoms/ions/molecules (Figure). Whereas top-down involves the mechanical
methods to crush/breaking of bulk into several parts to form nanoparticles (Figures)
 Nanomaterials Synthesis
Bottom-up approach Top-down approach

In general, bottom-up approach is meant by synthesis of nanoparticles by means of chemical

reactions among the atoms/ions/molecules (Figure a). Whereas top-down involves the mechanical
methods to crush/breaking of bulk into several parts to form nanoparticles (Figures b)