Nanochemistry

Introduction
• The word nano signifying very small objects of the range of 1–100 nm has
gained importance in the last two decades..
• The physical, chemical, electrical, optical and magnetic properties of
nanomaterials are significantly different from the properties of the same
material of bigger size. For example, a metal with a grain size of 10 nm is
seven times harder and tougher than its counterpart with the size of
hundreds of nanometers.
• Moreover, the nanomaterials have a relatively larger surface area than
ordinary materials and this has a significant effect on their physical
properties and chemical reactivities. It has been observed that certain
substances that are ordinarily unreactive become reactive in their nanoscale
form because of their high surface area.
• Nanoscience and Nanochemistry is the science of nanoparticles or the
particles whose size varies from 1 to 10 nm in at least one dimension.
 How much is a nanometer?

• One nanometer is equivalent to one billionth (one

thousand millionth) of a meter. These particles are not
visible to the human eye and can be seen only under a
powerful microscope. The size of various objects can help
to have a visual perception of a nano-sized objects.
 Human hair is about 100,000nm wide.
 Red blood cell is about 2000–5000nm wide.
 Human DNA is 2.5nm wide.
 Diameter of carbonnanotube is 1.0–1.3nm.
 Water molecule is about 0.3nm across.
 An ant is 4million nm big.
 Properties of Nanomaterials
• Optical properties: Optical properties are markedly affected by the
shape, size and surface characteristics, doping characteristics and
environmental interactions of the nanoparticles. For example, CdSe
nanoparticles show fluorescent emission over a broad range.
• Electrical properties: At nanoscale, the conductivity changes from
metal to semiconductors to insulators, that is, from high to low.
• Mechanical properties: Nanoparticles generally have good tensile
strength, elasticity and fracture resistance. They are therefore used as
fillers in polymers to improve their mechanical properties.
• Magnetic properties: Many substances such as gold and platinum
which are non-magnetic in bulk become magnetic at the nanosize.
Magnetic nanoparticles of Pd, Pt and Au can be obtained from non-
magnetic bulk materials.
 Self assembly
• Self-assembly is the basic principle underlying the bottom-up
approach that helps to synthesize nanomaterials and enables them to
organise into regular patterns with lowest energy configurations.
• Self-assembly enables very small atoms to be arranged into ordered
patterns or arrays to help them perform a particular function. The
components assemble or aggregate without the guidance of any
external force.
• For example, alkane thiols form self-assembled monolayers
(SAMS) on gold colloids. CdSe nanoparticles are formed by the
self-assembly of atoms into a stable crystalline form (molecular self-
assembly). A three-dimensional photonic crystal is formed by the
further self-assembly of CdSe nanoparticles (material self-
assembly).
Top-down & Bottom-up approaches
 Preparation of Nanomaterials

• The various methods generally employed for the synthesis of nanomaterials are as
follows:
1. Mechanical grinding: This method of synthesis of nanomaterials follows a top-
down approach. In this method, the nanoparticles are not synthesised by assembling
small particles but by the structural decomposition of larger particles by the use of
mechanical mills. This method is simple and inexpensive but causes environmental
pollution.
2. Wet chemical synthesis: Wet synthesis can follow the top-down approach in
which a single crystal is etched into nano-sized particles in aqueous solution.
Porous silicon is synthesised by electrochemical etching. It can also follow a
bottom-up approach where small particles agglomerate in a controlled manner to
form nanosized particles.
Sol gel process: It is a very popular method used for the preparation of oxide
nanomaterials. The sol–gel process involves hydrolysis followed by
condensation. A metal or metalloid employed as a precursor is dispersed in
acid or water to form a sol. Gel is obtained from this sol by the removal of
water.

• MOR+H2O MOH+ROH(hydrolysis).
• MOH+ROM MOM+ROH(condensation).
 Preparation of Nanomaterials
3. Gas–phase synthesis of nanomaterials:
• The conventional gas phase synthesis is the chemical vapor deposition
(CVD) method that canbe either homogeneous CVD or heterogeneous
CVD. In these synthetic routes, small clusters of nanoparticles are
produced because of condensation.
• In homogeneous CVD, the particles in the gaseous phase diffuse under the
influence of thermophoretic forces and deposit on the cold surface. These
deposits are either scrapped off to yield nanopowders or ‘particulate films’
are formed by depositing them onto the substrate.
Advantages:
• The size, shape and chemical composition of the nanomaterials can easily
be controlled.
• Substances formed are of high purity.
• There action mechanism is easily controllable.
 Nanomaterials:
1. Carbon nanotubes
• Carbon nanotubes are considered as allotropes of carbon
belonging to the fullerene family.
• A carbon nanotube consists of a sheet of carbon atoms that are
sp2-hybridised and have a hexagonal symmetry.
• Such a two-dimensional sheet is called graphene. A carbon
nanotube is produced by rolling a graphene sheet into a
cylindrical shape.
• The length is several times the width and the ratio of length to
diameter is of the order of 100; hence, carbon nanotubes are
considered as 1D structure.
 Properties of CNT:

• They have unique electronic and mechanical properties.

• They are100,000 times thinner than the humanhair.
• 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.
 Types of CNT:
• There are two types of CNTs:
 Single-walled (one tube)SWNT
 Multi-walled (several concentric tubes) MWNT
 Synthesis of CNT:
Carbon nanotubes are produced in the following manners:
• Evaporating graphite rods in a dynamic atmosphere of helium.
• 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.
• 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.
• 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 at750°Cfor half an hour; the product thus obtained is a
mixture of nanotubes.
 Applications of CNT:
• 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 arethe strongest known material.
Owing to their strength, they are widely used in manufacturing
reinforced plastics, car and aeroplane parts and in sports goods.
• 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.
• SWNTs find use in solar panels because of their tendency to absorb
ultraviolet/visible and near infrared light.
• MWNTs are used in lithium ion batteries and silicon-coated carbon
nanotubes are used as anodes for Li- ion batteries.
 2. Nanocrystals
• A nanocrystal is an inorganic entity in which the constituent atoms or ions
have a crystalline arrangement in at least one dimension and their size is less
than 100 nm. Semiconductor nanocrystals with size <10 nm are termed as
‘quantum dots’.
• Nanocrystals can be synthesised from vapor phase by crystallisation on
substrate through heterogeneous nucleation or by controlled homogeneous
nucleation in a super-saturated liquid phase.
• The agglomeration of the nanocrystal is prevented by capping them with
suitable capping or protecting agents.
• For example, nanocrystalline gold is prepared by the reduction of gold ions in
solution of citrate ions. The agglomeration of the colloidal sol is prevented
with electrostatic repulsion between the Au particles that are covered by
negatively charged citrate ions. The size of gold ions can also be controlled by
‘capping’ them with thiol molecules.
 Applications

Nanocrystals have a wide variety of applications, some of

which are as follows:
• In dye-sensitised solar cells.
• In medical imaging and as biotags for the identification of
genes.
• In the analysis of proteins and in the manufacture of drugs.
• In electronic industry, they find use in flat-panel displays,
magneto-optical memory chips, in optical and infrared
laser, etc.
• Zeolite nanoparticles are used to filter crude oil and
separate diesel from it.
 3. Quantum Dots
• Quantum dots are nanoparticles that range from 2to10 nm in diameter and are
made strictly from semiconductor materials such as chalcogenides(selenides and
sulfides) of metals such as cadmium or zinc (CdSe or ZnS).
• They can be prepared both by the top-down approach and the bottom-up
approach. The top-down approach includes milling and grinding, whereas in the
bottom-up approach one can use gas phase or liquid state approaches.
• All the general methods used for the preparation of nanomaterials can be applied
to the synthesis of quantum dots.
• The InP (indium group III and phosphorus group V) quantum dot can be
synthesised as follows:
 Indium oxalate, indium chloride or indium fluoride are used as precursors for
indium, and trimethylsilylphosphine is used as the precursor for phosphorus. A
mixture of trioctylphosphine oxide (TOPO) and trioctylphosphine acts as
colloidal stabilisers. The precursors are decomposed at a temperature greater
than 200°C. The nanocrystals are precipitated by adding methanol to the
dispersion.
 Properties

• The optical properties of quantum dots are

affected by the nature and area of the surface.
• Their properties change significantly when an
electron leaves the surface.
• Quantum dots emit photons under excitation and
these are visible to the human eye as light.
• By controlling their size, it is possible to monitor
their wavelength of emission and this in turn
determines the color of light perceived by the
human eye.
 Applications:
Quantum dots find diverse applications in varied fields:
• They are used in photolysis reactions and in the
manufacture of dye-synthesised solarcells.
• Similar to nanocrystals, quantum dots also find their
application as biological labels,bioconjugates and as drug
carriers.
• In the electronic industry, they are used for the preparation
of photovoltaic cells and other electrochromic devices.
• They also find use in environmental technologies for the
removal of pollutants from the environment (CdS
nanocrystals fix atmospheric carbondioxide).
 4. Nanowire
Nanowires have diameter of the order of a
nanometre (10–9m) and their length-to-width ratio is
greater than 1000; hence, they are also referred to as
a one-dimensional material. They can be of various
types:
• Metallic(e.g., Ni, Pt and Au).
• Semiconducting (e.g., silicon, gallium nitride and
indium phosphide).
• Insulating (e.g.,SiO2andTiO2).
• Molecules that have repeating molecular units. They
can be organic (DNA) or inorganic (Mo 6S9-xIx).
 Properties
• Depending upon the material with which the
nanowires are made, they can be metallic,
semiconductors or insulators.
• Nanowires behave like ballistic conductors. In
normal conductors, the speed of the conducting
electrons reduces because of collision with atoms,
whereas in ballistic conductors electrons travel
through the conductor without colliding with the
atoms.
• Nanowires can conduct efficiently without heating
the conductor wire.
 Applications:
• Nanowires conduct electricity; hence, they are used in making
miniature circuits for transistors and other basic electronic
devices such as junction diodes and logic gates.
• Nanowires are also used in quantum computers.
• Nanowires can also generate electricity from kinetic energy
(piezoelectric effect). Piezoelectric nanowires can be used in
future to provide power to nano-sized systems.
• Nano-sized devices such as nanorobots are made of
nanowires; these nanorobots are used to treat diseases such
as cancer.
• Used in thermoelectric cooling systems.
• Nanowires are used to link tiny components in extremely
small circuits.
 5. Carbonnanocones (nanohorns)

• They are conical structures made of carbon with one

nano- meter diameter at least in one dimension.
• Unlike nanowires, the height and base diameter in
nanocones is the same.
• Carbon nanocones are produced by the pyrolysis of
heavyoil with a plasma torch having temperature above
2000 °C.
• Nanocones can also be prepared by heating the graphite
surface with an intense short laser pulse so that some
carbon from the graphene sheet evaporates and other
atoms rearrange to form a conical structure.
 Haeckalites
• Named in the honour of the nineteenth century German
zoologist Ernst Haeckel, it consist of a layered structure of
pentagons, hexagons and heptagons.
• They can also be rolled like carbon nanotubes to give
tubular structures.
• The haeckalite nanotubes may have different structures
such as nanocoils, string of pearls, corrugated cylinders, etc.
• The stiffness and Young’s modulus of haeckalites is of the
same order of classical carbon nanotubes.
• Haeckalites find application in lithium storage, hydrogen
storage, electronic devices, in the medical field,
manufacture of sensors, etc.
 Surface Characterization Techniques

• To study the structure of nanomaterials they are

observed using electrons, photons, scanning probes,
ions, atoms, etc.
• The commonly used techniques are Brunauer–Emmet–
Teller (BET) surface area analysis, Fourier transform
infrared spectroscopy (FTIR), transmission electron
microscopy (TEM), scanning electron microscopy
(SEM), X-ray photoelectron spectroscopy
(XPS),powder X-ray diffraction (XRD), inductively
coupled plasma atomic emission spectroscopy (ICP-
AES), ultraviolet–visible spectroscopy, nuclear
magnetic resonance spectroscopy (NMR), etc.
 Applications of Nanomaterials

• Medicine: Nanomaterials are used in medicine as drug

carriers. Their large surface area enables them to load the drug
on them and their small size helps them to transport these
drugs into the cells, nuclei and across the membranes.
• Catalysis: The nanoparticles have large surface area and
hence provide higher catalytic activity. The nanosize of these
catalysts increases the reactive surface area, making them
extremely active and thereby economising their use.
• Environmental technologies: 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.
 Applications of Nanomaterials
• 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.
• Mechanics: Nanoparticles are used to improve the
performance of tyres and improve mechanical properties of
ceramics and alloys.
• 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.