UNIT V NANOCHEMISTRY

Basics - distinction between molecules, Nanoparticles and bulk materials; size-dependent

properties. nanoparticles: nano cluster, nano rod, nanotube(CNT) and nanowire. Synthesis:
precipitation, thermolysis, hydrothermal, solvothermal, electrodeposition, chemical vapour
deposition, laser ablation; Properties and applications

Session No 37: Basics of nano-materials and nanochemistry – features

Nanoscience and nanotechnology
• Nanoscience deals with the scientific study of objects with sizes in the 1 – 100 nm range in at
least one dimension.
• Nanotechnology deals with using objects in the same size range to develop products with
possible practical application. It is usually based on nanoscience insights.

Nanoscience and Nanochemistry

• Nanoscience is interesting in part of course because it by definition is new. But a more
profound and important reason is that it deals with objects which are only slightly larger than an
atom. This means that the properties of the objects can be influenced by direct manifestations of
quantum mechanics.
• It is also possible that nanoscale objects do behave just like as expected from (semi)classical
Physics, but the downgrading in size opens up possible new applications.
Nanotechnology is the creation of functional materials, devices, and systems through control of
matter on the nanometer (1 to 100 nm) length
scale and the exploitation of novel properties and phenomena developed at that scale.
• A scientific and technical revolution has begun that is based upon the ability to systematically
organize and manipulate matter on the nanometer length scale.
Defining Nanoscale
Cross section of human hair
Nano - Dwarf
Nano size: 1 nm = 10-6 Meter
Millimeter (mm) = 10-9 Meter
Combination of atoms or molecules to form objects of nanometer scale

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 Cross-sectional area of human hair
Characterization of nanomaterials
The properties of nanomaterials depend on size, crystal structure, surface characteristics and
particle size. The following instrumentation methods used to characterize nanomaterials,
 X ray diffraction
 Low energy electron diffraction
 Scanning electron microscopy
 Atomic force microscopy

Carbon nanostructures

Session No 38: Distinction between molecules, nano-particles and bulk materials –

illustration with examples.

1. Reduced Melting Point -- Nanomaterials may have a significantly lower melting point
or phase transition temperature and appreciably reduced lattice constants (spacing
between atoms is reduced), due to a huge fraction of surface atoms in the total
amount of atoms.
2. Ultra Hard -- Mechanical properties of nanomaterials may reach the theoretical strength,
which are one or two orders of magnitude higher than that of single crystals in the bulk
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 form. The enhancement in mechanical strength is simply due to the reduced probability
of defects.
3. Optical properties of nanomaterials can be significantly different from bulk crystals.
--- Semiconductor Blue Shift in adsorption and emission due to an increased band
gap.
Quantum Size Effects, Particle in a box.
--- Metallic Nanoparticles Color Changes in spectra due to Surface Plasmons
Resonances Lorentz Oscillator
Model.
4. Electrical conductivity decreases with a reduced dimension due to increased surface
scattering.
Electrical conductivity increases due to the better ordering and ballistic transport.
5. Magnetic properties of nanostructured materials are distinctly different from that of
bulk materials. Ferromagnetism disappears and transfers to superparamagnetism in
the nanometer scale due to the huge surface energy.
6. Self-purification is an intrinsic thermodynamic property of nanostructures and
nanomaterials due to enhanced diffusion of impurities/defects/dislocations to the
nearby surface.
7. Increased perfection enhances chemical stability.

Two primary factors cause nanomaterials to behave significantly differently than bulk materials:
surface effects (causing smooth properties scaling due to the fraction of atoms at the surface) and
quantum effects (showing discontinuous behavior due to quantum confinement effects in
materials with delocalized electrons). These factors affect the chemical reactivity of materials, as
well as their mechanical, optical, electric, and magnetic properties. The fraction of the atoms at
the surface in nanoparticles is increased compared to microparticles or bulk. Compared to
microparticles, nanoparticles have a very large surface area and high particle number per unit
mass. For illustration, one carbon microparticle with a diameter of 60 µm has a mass of 0.3 µg
and a surface area of 0.01 mm2. The same mass of carbon in nanoparticulate form, with each
particle having a diameter of 60 nm, has a surface area of 11.3 mm2 and consists of 1 billion
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nanoparticles. For example, the melting temperature of 3 nm gold nanoparticles is more than 300
degrees lower than the melting temperature of bulk gold. An example of a class of materials that
clearly exploits quantum effects is quantum dots - synthesized nanostructures with sizes as small
as a few nanometers. The electronic behavior of quantum dots is similar to that of individual
atoms or small molecules, and quantum dots are regarded as akin to artificial atoms Nano
materials have superior properties than bulk materials.
Bulk (eg. Gold) Nano (eg. Gold)
1. Lustrous–Shiny surface when polished. 1. Vary in appearance depending on size &
2. Malleable–Can be hammered, bent or shape of cluster.
rolled®any desired shape. 2. Are never gold in colour!.
3. Ductile–Can be drawn out into wires 3. Are found in a range of colours.
4. Yellow colour when in a mass 4. Are very good catalysts.
5. Heat & electricity conductor 5. Are not ―metals‖ but are semiconductors.
6. High densities 6. Melts at relatively low temperature (~940º C).
7. High melting point (1080ºC) 7. Size & Shape of the nanoparticles determines
8. Tough with high tensile strength the color.
9. Inert-unaffected by air and most reagents 8. For example; Gold particles in glass:
25 nm — Red reflected
50 nm — Green reflected
(Unexpected visible properties & they
are small enough to scatter visible
light rather than absorb)

Session No 39: Size-dependent properties- nano-particles: nano-clusters etc.

Size dependent properties nanomaterials
Nanoparticles are of great scientific interest as they are, in effect, a bridge between bulk
materials and atomic or molecular structures. A bulk material should have constant physical
properties regardless of its size, but at the nano-scale size-dependent properties are often
observed. Thus, the properties of materials change as their size approaches the nanoscale and as
the percentage of atoms at the surface of a material becomes significant. For bulk materials
larger than one micrometer (or micron), the percentage of atoms at the surface is insignificant in
relation to the number of atoms in the bulk of the material. The interesting and sometimes
unexpected properties of nanoparticles are therefore largely due to the large surface area of the
material, which dominates the contributions made by the small bulk of the material.

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Nanoparticles often possess unexpected optical properties as they are small enough to confine
their electrons and produce quantum effects.
For example gold nanoparticles appear deep-red to black in solution. Nanoparticles of yellow
gold and grey silicon are red in color. Gold nanoparticles melt at much lower temperatures (~300
°C for 2.5 nm size) than the gold slabs (1064 °C)
Other size-dependent property changes: The high surface area to volume ratio of nanoparticles
provides a tremendous driving force for diffusion, especially at elevated temperatures. Sintering
can take place at lower temperatures, over shorter time scales than for larger particles. In theory,
this does not affect the density of the final product, though flow difficulties and the tendency of
nanoparticles to agglomerate complicates matters. Moreover, nanoparticles have been found to
impart some extra properties to various day to day products. For example, the presence of
titanium dioxide nanoparticles imparts what we call the self-cleaning effect, and, the size being
nano-range, the particles cannot be observed. Zinc oxide particles have been found to have
superior UV blocking properties compared to its bulk substitute. This is one of the reasons why it
is often used in the preparation of sunscreen lotions, and is completely photostable.

Session No 40: Nano-rod, nano-tube(CNT) and nano-wire (CNT).

Classification of nano structures materials
Nano particle;
1. Nano cluster
2. Nano rod
3. Nano tube and
4. Nanowires
Nanoclusters
Nanoclusters constitute an intermediate state of matter between molecules and solids.
Nanocluster sizes range from sub-nanometer to about 10 nanometres in diameter and are of
technological interest in numerous areas of applied science (e.g. materials science, catalysis and
opto-electronics). Often one differentiates between:
(i) nanoclusters consisting of up to a couple of hundred atoms, and

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 (ii) larger aggregates containing 103 or more atoms which are more often called
nanoparticles.
The properties of nanoparticles gradually approach those of bulk materials or extended surfaces,
i.e. are scalable with size. Nanoclusters, however, have properties and structures which are very
sensitive to their composition and size (i.e. ―every atom counts‖) which can lead to new and
interesting properties not realised in the corresponding bulk material.

Cluster model
Nanorods
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. Nanorods are produced by direct chemical synthesis.
Combinations of ligands act as shape control agents and bond to different facets of the nanorod
with different strengths. This allows different faces of the nanorod to grow at different rates,
producing an elongated object.
One potential application of nanorods is in display technologies, because the reflectivity of the
rods can be changed by changing their orientation with an applied electric field. Another
application is for micro-electromechanical systems (MEMS). Nanorods, along with other noble
metal nanoparticles, also function as the agnostic agents. Nanorods absorb in the near IR, and
generate heat when excited with IR light. This property has led to the use of nanorods as cancer
therapeutics. Nanorods can be conjugated with tumor targeting motifs and ingested. When a
patient is exposed to IR light (which passes through body tissue), nanorods selectively taken-up
by tumor cells are locally heated, destroying only the cancerous tissue while leaving healthy cells
intact.

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 Nanorod
Nano tube (Carbon nanotubes (CNT))
A carbon nanotube (CNT) is a miniature cylindrical carbon structure that has hexagonal graphite
molecules attached at the edges.
Nanotubes look like a powder or black soot, but they're actually rolled-up sheets of graphene that
form hollow strands with walls that are only one atom thick. Nanotubes, which are sometimes
called bulky tubes, were developed from the Fullerene, a structure that is similar to the geodesic
domes.
Nanotubes, which are grown in a laboratory, are strong and exhibit many thermal and electrical
properties that are desirable to chip makers. Carbon nanotubes have the potential to be used as
semiconductors, for example, potentially replacing silicon in a wide variety of computing
devices.
Nanotubes can be characterized by their number of concentric cylinders, cylinder radius and
cylinder length. Some nanotubes have a property called chirality, an expression of longitudinal
twisting. Multiple nanotubes can be assembled into microscopic mechanical systems called
nanomachines.

Corbon nanotube
Nanowires
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. Alternatively,
nanowires can be defined as structures that have a thickness or diameter constrained to tens of
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nanometers or less and an unconstrained length. At these scales, quantum mechanical effects are
important — which coined the term "quantum wires". Many different types of nanowires exist,
including metallic (e.g., Ni, Pt, Au), semiconducting (e.g., Si, InP, GaN, etc.), and insulating
(e.g., SiO2, TiO2). Molecular nanowires are composed of repeating molecular units either organic
(e.g. DNA) or inorganic (e.g. Mo6S9-xIx).

Nanowire

Session No: 41 Synthesis: of nano-materials: precipitation, thermolysis, hydrothermal and

solvothermal methods.
Synthesis of nanomaterials
Top-down and bottom-up are two approaches for the manufacture of products. These terms were
first applied to the field of nanotechnology by the Foresight Institute in 1989 in order to
distinguish between molecular manufacturing (to mass-produce large atomically precise objects)
and conventional manufacturing (which can mass-produce large objects that are not atomically
precise). Bottom-up approaches seek to have smaller (usually molecular) components built up
into more complex assemblies, while top-down approaches seek to create nanoscale devices by
using larger, externally controlled ones to direct their assembly.
The top-down approach often uses the traditional workshop or microfabrication methods where
externally controlled tools are used to cut, mill, and shape materials into the desired shape and
order. Micropatterning techniques, such as photolithography and inkjet printing belong to this
category.
Bottom-up approaches, in contrast, use the chemical properties of single molecules to cause
single-molecule components to (a) self-organize or self-assemble into some useful conformation,
or (b) rely on positional assembly. These approaches utilize the concepts of molecular self-
assembly and/or molecular recognition. See also Supramolecular chemistry. Such bottom-up

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approaches should, broadly speaking, be able to produce devices in parallel and much cheaper
than top-down methods, but could potentially be overwhelmed as the size and complexity of the
desired assembly increases.

Nanomaterials deal with very fine structures: a nanometer is a billionth of a meter. There
are two general approaches to the synthesis of nanomaterials and the fabrication of
nanostructures,
Synthesis nanomaterials
Bottom up approach Top-down approach
1. Precipitation 1. Laser ablation method.
2. Thermolysis 2. Chemical vapour deposition method.
 Solvothermal method 3. Electrodeposition
 Hydrothermal method

Bottom up approach
1. Precipitation
Precipitation method based on the reduction of metal salts in appropriate solvents with variety of
reducing agents.
Alcohol, glycol, metal borohydride, Phosphonium chloride are some of the reducing agents
involved in this method.
For example reduction of chloroaurate ions in aqueous solution by citric acid or sodium boro
hydride results in gold hydro sol with particle size in the range of 10-640 A.
Reduction
Chloroaurite ions + Sodium borohydride---------------- Gold hydrosol

Sols of metals and semiconductors nanoparticles are stabilized by the presence of ligand or
stabilizing agent. Long chain amines, thiol or polymers can be act as a stabilizing agents.

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Ex: PVA-PVP which prevent the aggregation of the particle
Arrested precipitation or kinetic control of precipitation has been adopted to prepare
semiconductor nano crystal of CdS, CdSe, Zno, Zns, HgTe, Pbs, Cus, Cu2 S, AgI and TiO2.

2. Thermolysis
Nanoparticles can also be made by decomposing solids or liquids at high temperatures having
metal cations, or molecular anions or metal organic compounds. This is called thermolysis.
For example Li particles can be made by decomposing lithium azide, LiN3.
Hydrothermal synthesis
Hydrothermal synthesis includes the various techniques of crystallizing substances from high-
temperature aqueous solutions at high vapor pressures; also termed "hydrothermal method".
Hydrothermal synthesis can be defined as a method of synthesis of single crystals that depends
on the solubility of minerals in hot water under high pressure. The crystal growth is performed in
an apparatus consisting of a steel pressure vessel called an autoclave, in which a nutrient is
supplied along with water. A temperature gradient is maintained between the opposite ends of
the growth chamber. At the hotter end the nutrient solute dissolves, while at the cooler end it is
deposited on a seed crystal, growing the desired crystal.
Solvo thermal synthesis
Solvothermal synthesis is a method of producing chemical compounds. It is very similar to the
hydrothermal route (where the synthesis is conducted in a stainless steel autoclave), the only
difference being that the precursor solution is usually not aqueous (however, this is not always
the case in all literature uses of the expression). Using the solvothermal route gains one the
benefits of both the sol-gel and hydrothermal routes. Thus solvothermal synthesis allows for the
precise control over the size, shape distribution, and crystallinity of metaloxide nanoparticles or
nanostructures. These characteristics can be altered by changing certain experimental parameters,
including reaction temperature, reaction time, solvent type, surfactant type, and precursor type.
Solvothermal synthesis has been used in laboratory to make nanostructured titanium dioxide,
graphene, carbon and other materials.

Session No: 42 Laser ablation techniques of nano-material synthesis.

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Top down’ approach
(a) Laser ablation method.
(b) Chemical vapour deposition method.
(c) Electrodeposition
Laser ablation method
It is the process of removing material from a solid (or occasionally liquid) surface by irradiating
it with a laser beam. At low laser flux, the material is heated by the absorbed laser energy and
evaporates or sublimates. At high laser flux, the material is typically converted to a plasma.
Usually, laser ablation refers to removing material with a pulsed laser, but it is possible to ablate
material with a continuous wave laser beam if the laser intensity is high enough.
Session No: 43 Chemical Vapour Deposition(CVD) method of synthesis.
Chemical vapour deposition method
Chemical vapor deposition (CVD) is a chemical process used to produce high-purity, high-
performance solid materials. 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.
Frequently, volatile by-products are also produced, which are removed by gas flow through the
reaction chamber.
Microfabrication processes widely use CVD to deposit materials in various forms, including:
monocrystalline, polycrystalline, amorphous, and epitaxial. These materials include: silicon,
carbon fiber, carbon nanofibers, fluorocarbons, filaments, carbon nanotubes, SiO2, silicon-
germanium, tungsten, silicon carbide, silicon nitride, silicon oxynitride, titanium nitride, and
various high-k dielectrics. CVD is also used to produce synthetic diamonds.
Electrodeposition:
Also knows as electroplating, electroplating is using a small sheet of metal in an electrocytic cell
to coat another object. It is used to protect objects from damage against rusting and corrosion of
metals.
The Chemistry behind electroplating is this: the item to be plated by the metal gets the
negative charge and is put into a salt solution of the metal being used to plate the object. The
metal being used to plate the item has a positive charge and is placed in the same solution.

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Therefore, the object to be plated is the cathode, and the metal being used to plate the item is the
anode. Because of this, electroplating is a electrolytic cell since the electrons are flowing from
positive to negative, where the metal to be plated is being reduced and the metal being used in
the process is being oxidized. With the electrons flowing, it is just the law of attraction. The
positive ions from the salt solution and the metal being used to plate "stick" onto the object being
plated since it has a negative charge. The thickness of the metal plating depends on how long you
leave it in the solution, and the flow of electrons.

Session No: 44 Properties and applications of nano-materials.

Properties of Nanomaterials
 Mechanical properties: The mechanical properties of carbon nanotubes in the radial
(transverse) direction. Carbon nanotubes are one of the strongest materials in nature. Carbon
nanotubes (CNTs) are long hollow cylinders of graphene. Although graphene sheets have
2D symmetry, carbon nanotubes by geometry have different properties in axial and radial
directions. It has been shown that CNTs are very strong in the axial direction. Young's
modulus on the order of 270 - 950 GPa and tensile strength of 11 - 63 GPa were obtained.
On the other hand, there was evidence that in the radial direction they are rather soft. The
first transmission electron microscope observation of radial elasticity suggested that even
the van der Waals forces can deform two adjacent nanotubes. Later, nanoindentations with
atomic force microscope were performed by several groups to quantitatively measure radial
elasticity of multiwalled carbon nanotubes and tapping/contact mode atomic force
microscopy was also performed on single-walled carbon nanotubes.
 Catalytic Properties: Functionalized metal nanoparticles are more stable in solution
compared to non-functionalized metal nanoparticles. In liquid solutions, the metal
nanoparticles are close enough together to be affected by van der Waals force. If there isn’t
anything to oppose these forces, then the nanoparticles will aggregate, which will lead to a
decrease in catalytic activity by lowering the surface area. For organometallic functionalized
nanoparticles, ligands are coordinated to the metal center to prevent aggregation. Using
different ligands alters the properties and sizes of the nanoparticle catalysts. Nanoparticles

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 can also be functionalized with polymers or oligomers to sterically stabilize the
nanoparticles by providing a protective layer that prevents the nanoparticles from interacting
with each other. Alloys of two metals, called bimetallic nanoparticles, are used to create
synergistic effects on catalysis between the two metals.
 Magnetic Properties: In magnetic nanoparticles, the energy of magnetic anisotropy may be
that small that the vector of magnetization fluctuates thermally; this is called
superparamagnetism. Such a material is free of remanence, and coercitivity. Touching
superparamagnetic particles are loosing this special property by interaction, except the
particles are kept at distance. Combining particles with high energy of anisotropy with
superparamagnetic ones leads to a new class of permanent magnetic materials.
 Optical Properties: Distributions of non-agglomerated nanoparticles in a polymer are used
to tune the index of refraction. Additionally, such a process may produce materials with
non-linear optical properties. Gold or CdSe nanoparticles in glass lead to red or orange
coloration. Semi-conducting nanoparticles and some oxide-polymer nanocomposites exhibit
fluorescence showing blue shift with decreasing particle size.

Applications of nanomaterial
Since nanomaterials possess unique, beneficial chemical, physical, and mechanical properties,
they can be used for a wide variety of applications. These applications include, but are not
limited to, the following:
 Next-Generation Computer Chips: The microelectronics industry has been emphasising
miniaturisation, whereby the circuits, such as transistors, resistors, and capacitors, are
reduced in size.
 Kinetic Energy (KE) Penetrators with Enhanced Lethality: The Department of Defense
(DoD) is currently using depleted-uranium (DU) projectiles (penetrators) for its lethality
against hardened targets and enemy armoured vehicles.
 Better Insulation Materials: Nanocrystalline materials synthesised by the sol-gel technique
result in foam like structures called "aerogels." These aerogels are porous and extremely
lightweight; yet, they can loads equivalent to 100 times their weight. Aerogels are composed
of three-dimensional, continuous networks of particles with air (or any other fluid, such as a

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 gas) trapped at their interstices. Since they are porous and air is trapped at the interstices,
aerogels are currently being used for insulation in offices, homes, etc.
 Phosphors for High-Definition TV: The resolution of a television, or a monitor, depends
greatly on the size of the pixel. These pixels are essentially made of materials called
"phosphors," which glow when struck by a stream of electrons inside the cathode ray tube
(CRT). The resolution improves with a reduction in the size of the pixel, or the phosphors.
 Low-Cost Flat-Panel Displays: Flat-panel displays represent a huge market in the laptop
(portable) computers industry. However, Japan is leading this market, primarily because of
its research and development efforts on the materials for such displays.
 Tougher and Harder Cutting Tools: Cutting tools made of nanocrystalline materials, such as
tungsten carbide, tantalum carbide, and titanium carbide, are much harder, much more wear-
resistant, erosion-resistant, and last longer than their conventional (large-grained)
counterparts.
 Elimination of Pollutants: Nanocrystalline materials possess extremely large grain
boundaries relative to their grain size. Hence, nanomaterials are very active in terms of their
of chemical, physical, and mechanical properties. Due to their enhanced chemical activity,
nanomaterials can be used as catalysts to react with such noxious and toxic gases as carbon
monoxide and nitrogen oxide in automobile catalytic converters and power generation
equipment to prevent environmental pollution arising from burning gasoline and coal.
 High Energy Density Batteries: Conventional and rechargeable batteries are used in almost
all applications that require electric power. These applications include automobiles, laptop
computers, electric vehicles, next-generation electric vehicles (NGEV) to reduce
environmental pollution, personal stereos, cellular phones, cordless phones, toys, and
watches. The energy density (storage capacity) of these batteries is quite low requiring
frequent recharging. The life of conventional and rechargeable batteries is also low.
Nanocrystalline materials synthesised by sol-gel techniques are candidates for separator
plates in batteries because of their foam-like (aerogel) structure, which can hold considerably
more energy than their conventional counterparts.

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 High-Sensitivity Sensors: Sensors employ their sensitivity to the changes in various
parameters they are designed to measure. The measured parameters include electrical
resistivity, chemical activity, magnetic permeability, thermal conductivity, and capacitance.
 Automobiles with Greater Fuel Efficiency: Currently, automobile engines waste considerable
amounts of gasoline, thereby contributing to environmental pollution by not completely
combusting the fuel. A conventional spark plug is not designed to burn the gasoline
completely and efficiently. This problem is compounded by defective, or worn-out, spark
plug electrodes.
 Aerospace Components with Enhanced Performance Characteristics: Due to the risks
involved in flying, aircraft manufacturers strive to make the aerospace components stronger,
tougher, and last longer. One of the key properties required of the aircraft components is the
fatigue strength, which decreases with the component’s age.
 Better and Future Weapons Platforms
 Longer-Lasting Satellites
 Longer-Lasting Medical Implants
 Ductile, Machinable Ceramics
 Large Electrochromic Display Devices.

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