Nanochemistry

Department of Chemistry
National Institute of Technology Hamirpur
 Nano……Nanoparticles……Nanoscience ?

1 nm = 1 x 10-9 m

Dimensions-size of 1 - 100 nm. i.e. of nanoscale (1 x 10-9 m to 1 x 10-7 m)

An individual atom has a diameter ???

Nanoparticles may contain just a few hundred atoms,

They are very very small ! Nanoparticles range in size from 1 nm to 100 nm.

Typical nanoparticles are roughly spherical in shape, but the

surface area to volume ratio is extremely important.
 Surface area to volume ratio in nanodimensions

Surface area : Volume ratio for selected nm cube sizes

length of area of one total surface volume of surface area /
side nm face nm2 area nm2 cube nm3 volume nm-1
1 1 6 1 6.0
10 100 600 1 000 0.6
100 10 000 60 000 1 000 000 0.06
1000 1 000 000 6 000 000 1 000 000 000 0.006
 If L = length of one side of cube, L x L =area of one face = L2,
Total surface area = 6L2
Volume = L X L x L = L3,
Therefore, surface area / volume ratio = 6L2 / L3 = 6/L

So, giving a general rule, as L decreases, surface / volume ratio increases.

Spherical nanoparticles
surface area of a sphere = 4πr2
volume of sphere = 4/3πr3
surface area / volume ratio = 4πr2 / 4/3πr3 = 3/r

The smaller the particle the greater the surface area to volume ratio.

Importance
Nanoparticles have a very high surface to volume ratio and this gives them special
properties different from the bulk material
•Extra chemical reactivity compared to the bulk material,
•Less of a material like a catalyst is needed in a chemical process
What is Nanoscience ?
Nanoscience is the branch of science concerned with the development and
production and uses of materials whose basic components are of nanoscale size,
i.e. ~1 - 100 nm in size.

What is Nanotechnology ?
Nanotechnology involves methods for transforming matter, energy and
information based on nanometre scale (nanosized) components.

It involves techniques that produces materials with characteristic features

with particle sizes of ~1 - 100 nm and involves advanced microfabrication
techniques.

What are Nanostructures ?

Nanostructures are material structures assembled from layers or clusters of atoms
of nanoscale size i.e. ~1-100 nm

What are Nanomaterials?

Nanomaterials is a general word for any material that has a composition based on
nanoparticle units e.g. nanoparticles of silver, carbon nanotubes etc.
 Dimensions of nanomaterials
Based on the number of dimensions of a materials outside the range of nanoscale (1-100 nm)

Zero-Dimensions (0-D) One-Dimensions (1-D) Two-Dimensions (2-D) Three-Dimensions (3-D)

All dimentions are One dimension is Two dimensions are Not confined to
within nanoscale range outside of nanoscale outside of nanoscale nanoscale in any
(1-100 nm). range. range. dimensions.
Means….. This class of This class of
No dimensions are nanomaterials This class of nanomaterials include-
larger than 100 nm include-nanotubes, nanomaterials bulk powder, bundles of
Example: nanorods, nanowires include- nanofilms, nanostructures such as
nanoparticles etc. nanocaotings, etc. nanorods/wires etc.
What is NANOCHEMISTRY ?

Nanochemistry is a branch of nanoscience, deals with the chemical applications of

nanomaterials in nanotechnology.

Nanochemistry involves the study of the synthesis and characterisation of materials

of nanoscale size.
An allotrope of carbon Prepared by vaporizing
graphite
Molecule of formula C60
Fullerene or buckyball
Generally mixture of
Named as Buckminster various fullerenes are
fullerene in honor of formed
Buckminster Fuller
Which are separated by
Fuller’ene’ because of
chromatography methods
double bond

Each carbon atom forms Properties: thermally

three sigma bonds with very stable, electrically
SP2 hybrid orbitals and insulating but can be
one pi bond with made
remaining P orbital conducting/superconducti
ng by doping
Composed of hexagons
and pentagons
Applications:
Found in various superconductor,
compositions of C atoms electronic devices etc
such as C70 ,C50 ,C36……..
 Types of Fullerene
• Buckyball clusters: smallest member is C20 (unsaturated version of dodecahedrane)
and the most common is C60
• Nanotubes: hollow tubes of very small dimensions, having single or multiple walls;
potential applications in electronics industry
• Megatubes: larger in diameter than nanotubes and prepared with walls of different
thickness; potentially used for the transport of a variety of molecules of different
sizes
• Polymers: chain, two-dimensional and three-dimensional polymers are formed
under high pressure high temperature conditions
• Nano"onions": spherical particles based on multiple carbon layers surrounding a
buckyball core; proposed for lubricants
• Linked "ball-and-chain" dimers: two buckyballs linked by a carbon chain
• fullerene rings.

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 Chemistry of Fullerene
• Fullerenes are stable, but not totally unreactive.
• The sp2-hybridized carbon atoms must be bent to form the
closed sphere or tube, which produces angle strain.
• The characteristic reaction of fullerenes is
electrophilic addition at 6,6-double bonds, which reduces
angle strain by changing sp2-hybridized carbons into sp3-
hybridized ones.
• The change in hybridized orbitals causes the bond angles to
decrease from about 120° in the sp2 orbitals to about 109.5° in
the sp3 orbitals.
• This decrease in bond angles allows for the bonds to bend less
when closing the sphere or tube, and thus, the molecule
becomes more stable.
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 Graphene is an allotrope of carbon
Graphene Structure is one-atom-thick planar
sheets of sp2-bonded carbon atoms
Densely packed in a honeycomb
crystal lattice.
Term graphene was coined as a
combination of graphite and the
suffix –ene
Graphene is most easily visualized
as an atomic-scale chicken wire
made of carbon atoms and their
bonds.
The crystalline or "flake" form of
Graphene is an graphite consists of many graphene
atomic-scale honeycomb lat
tice
sheets stacked together.
made of carbon atoms.
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 Important Features
• The carbon-carbon bond length in graphene is about 0.142
nanometers.
• Graphene sheets stack to form graphite with an interplanar
spacing of 0.335 nm, which means that a stack of 3 million
sheets would be only one millimeter thick.
• Graphene is the basic structural element of some carbon
allotropes including graphite, charcoal, carbon nanotubes and
fullerenes.
• It can also be considered as an indefinitely large aromatic
molecule, the limiting case of the family of flat
polycyclic aromatic hydrocarbons.

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 Graphene
Graphene is a flat honeycomb lattice made of a single layer of carbon atoms,
which are held together by a backbone of overlapping sp2 hybrids bonds

Graphene conducts heat

It is not only one of better than all other
the thinnest but also materials.
strongest materials

It is a great conductor It is optically transparent

of electricity.

The extraordinary characteristics of graphene originate from

the 2p orbitals, which form the π state bands that delocalize
over the sheet of carbons that constitute graphene.
 Graphene is light—it weighs just 0.77 milligrams per square meter.

Since it is a single 2D sheet, it has the highest surface area of all materials

When left to themselves, graphene sheets will stack and form graphite, which
is the most stable 3D form of carbon under normal conditions.

Graphene sheets are flexible, and in fact graphene is the most stretchable
crystal—you can stretch it up to 20% of its initial size without breaking it.

Finally, perfect graphene is also highly impermeable, and even helium atoms
cannot go through it.
 Graphene Synthesis

Mechanical exfoliation is the simplest of the preparation methods for graphene

Chemical Vapor Deposition (CVD)

 Graphene: Applications
Due to the extraordinary properties of graphene, it is suitable for a wide spectrum of
applications ranging from
Electronics to
Optics,
Sensors, and
Biodevices.
 Carbon Nanotubes (CNTs)

CNTs are kind of They are 1 dimensional

cylindrical fullerenes allotropes of carbon.

CNTs are cylindrical large molecules consisting of a hexagonal arrangement of

hybridized carbon atoms,

CNTs may by formed by rolling up a single sheet of graphene (single-walled

carbon nanotubes, SWCNTs)
or
by rolling up multiple sheets of graphene (multiwalled carbon nanotubes,
MWCNTs).
What Are Carbon
Nanotubes?
• CNT can be described as a
sheet of graphite rolled into a
cylinder
• Constructed from hexagonal
rings of carbon
• Can have one layer or multiple
layers
• Can have caps at the ends
making them look like pills

Information retrieved from: http://www.photon.t.u-tokyo.ac.jp/~maruyama/agallery/agallery.html

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 Synthesis: overview
• Commonly applied techniques:
• Chemical Vapor Deposition (CVD)
• Arc-Discharge
• Laser ablation

• Techniques differ in:

• Type of nanotubes (SWNT / MWNT / Aligned)
• Catalyst used
• Yield
• Purity
Synthesis methods
• Arc discharge
During this process, the carbon contained in the negative electrode sublimates because
of the high-discharge temperatures (above 1,700 °C).
It produces both single- and multi-walled nanotubes with lengths of up to 50
micrometers
• Laser ablation
During this process, a pulsed laser vaporizes a graphite target in a high-temperature
reactor while an inert gas is bled into the chamber. Nanotubes develop on the cooler
surfaces of the reactor as the vaporized carbon condenses.
 CVD
During CVD, a substrate is prepared with a layer of metal catalyst particles, most
commonly nickel, cobalt, iron, or a combination

The substrate is heated to approximately 700 °C. To initiate the growth of nanotubes,
two gases are bled into the reactor: a process gas (such as ammonia, nitrogen or
hydrogen) and a carbon-containing gas i.e. hydrocarbon (such as acetylene, ethylene,
ethanol or methane).

Hydrocarbons on hot metallic surface decompose into hydrogen and carbon species.
Carbon atoms precipitate and crystallize on the metal surface
Some important properties include
• Extraordinary electrical conductivity, heat conductivity, and
mechanical properties.
• They are probably the best electron field-emitter known, largely due
to their high length-to-diameter ratios

Key application areas

• Field Emitters/Emission
• Conductive or reinforced plastics
• Molecular electronics: CNT based non-volatile RAM
• CNT based transistors
• Energy Storage
• CNT based fibers and fabrics
• CNT based ceramics
• Biomedical applications etc ...
 Depending on the nature of folding of sheets along different axes they
are majorly of 3 types- Zigzag, Armchair and Chiral.

Important
Nanotubes as well as fullerene have their atoms settled on the surface allowing
these to only interact with molecules that surround them. As for graphene, all of
its atoms are also on the surface but can be easily accessed from both sides,
allowing more interaction between the molecules that surround it.
Thank you