Unit 3 Nanochemistry updated 2024
Unit 3 Nanochemistry updated 2024
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NANOCHEMISTRY
Master title style
Topics to be covered
1 Introduction - Basics of Nanochemistry – Nano-technology – Nano-science –
Nano-Chemistry features.
2 Difference between Nanomaterials and Bulk Materials.
• Atoms are very small and the diameter of a single atom can vary
from 0.1 to 0.5 nm.
Nanomaterials
• Nanomaterials are the materials having components with size less than 100 nm at least in
one dimension.
• Nanomaterials, in one dimension, are layers such as a thin films or surface coatings.
• Nanomaterials, in two dimensions, are tubes such as nanotubes and nanowires.
• Nanomaterials, in three dimension, are particles like precipitates, colloids and quantum
dots.
Basics
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Nanochemistry (or) Nanoscience
Nanoscience is defined as the study of phenomena and
manipulation of materials at atomic, molecular and
macromolecular scales.
Nanotechnology
Nanotechnology is defined as the design,
characterization, production and applications of
structures, systems and devices by controlling size and
shape at 10-9 m scale or the single atomic level.
Types of nanomaterials
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Nanomaterials can be categorized into four types such as:
1. Inorganic-based nanomaterials - Examples of metal-based inorganic
nanomaterials are silver (Ag), gold (Au), aluminum (Al), cadmium (Cd), copper
(Cu), iron (Fe), zinc (Zn), and lead (Pb) nanomaterials, whereas examples of metal
oxide-based inorganic nanomaterials are zinc oxide (ZnO), copper oxide (CuO),
magnesium aluminum oxide (MgAl2O4), titanium dioxide (TiO2), cerium oxide
(CeO2), iron oxide (Fe2O3), silica (SiO2), and iron oxide (Fe3O4), etc.
2. Carbon-based nanomaterials - Examples: graphene, fullerene, single-walled
carbon nanotube, multiwalled carbon nanotube, carbon fiber, an activated carbon,
and carbon black.
3. Organic-based nanomaterials - The organic-based nanomaterials are formed
from organic materials excluding carbon materials, for instance, dendrimers,
cyclodextrin, liposome, and micelle. and
4. Composite-based nanomaterials - any combination of metal-based, metal oxide-
based, carbon-based, and/or organic-based nanomaterials, and these
nanomaterials have complicated structures like a metal-organic framework.
Difference between Nanomaterials and
Bulk Master
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Disadvantages
•High energy required.
•Extensive long period of milling time.
•Contamination of powder due to steel balls.
•Very sensitive microstructure can be grinded.
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Applications
•This method is preferred to blend aluminium with magnesium and
carbon in order to alter its chemical properties and combustion
behavior.
•Preparation of elemental powder of aluminium (Al) and beta-silicon
carbide (β-SiC).
•Recently the ceramic nanoparticles WC-14% magnesium oxide (MgO)
has been prepared.
•It is widely used method for mechanical alloying to produce amorphous
alloys such as metal-metal, transition metal-metalloid, and metal-
carbon systems for various purposes.
Mechanochemical synthesis
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• Mechanochemical synthesis adopts the efficient mixing of reactants
using ball milling without or with a very small quantity of solvents. This
synthesis is also energy- and time-efficient. Therefore,
mechanochemical processing is regarded as an environmentally-friendly.
• Mechanical methods include mechanical grinding, high-energy ball
milling, mechanical alloying (MA), and reactive milling. The advantages
of these techniques are that they are simple, require low-cost
equipment, and, provided that a coarse feedstock powder can be made,
the powder can be processed.
Mechanochemical synthesis
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• It is based on repeated deformation, welding, and
fracture of the mixture of reactants.
• Different chemical modifications are produced at the
interface of nano-sized particles during the milling
process.
• Generally, high temperature is required to precede
chemical reactions for various purposes like to separate
reacting phases from the product phase.
• Nanoparticles can be obtained using a ball mill at low
temperatures without any use of external heating.
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• In mechanochemical method of synthesis, the starting materials
(like sodium carbonate and chloride hexahydrate for Fe3O2
nanoparticles synthesis) are mixed stichometrically and milled.
• The nanoparticles produced are surrounded with the byproduct
material, which is dispersed in soluble salt matrix. Afterwards the
byproduct is removed by washing with suitable solvent and
subsequently the particles dried at 105 °C for 12hr.
Advantages: Simple and efficient method of nanoparticle preparation.
Disadvantages
• The microstructures (nanostructures/nanoparticles) formed are
highly sensitive to grinding condition and may get affected from
unwanted contamination from milling media and atmosphere.
• For the preparation of smaller particles (smaller than 20 nm) long
term milling is required.
•
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Applications
• Synthesis of ferric oxide (Fe2O3) nanoparticles.
• Widely used for nanocrystalline particle synthesis.
• Effective method for metal nanoparticles (usually noble
metals) preparation with improved structural and
catalytic properties.
• Formation of alloying at low temperature.
• Nanomaterial preparation such as silver–aluminum mixed
oxide catalyst (Ag/Al2O3).
LaserMaster
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• Laser ablation or photoablation (also called laser blasting) is the
process of removing material from a solid (or occasionally liquid)
surface by irradiating it with a laser beam.
The high power of the laser beam induces large light absorption on the
surface of target, which makes temperature of the absorbing
material increase rapidly. As a result, the material on the surface
of target vaporizes into laser plume.
Laser ablation
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Key parameters:
• Laser type (e.g., Nd:YAG, (Neodymium-doped Yttrium Aluminum Garnet laser)
Ti:Sapphire, copper vapor)
• Laser pulse duration and energy
• Liquid type and volume
• Presence or absence of surfactant
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Advantages
1. Relatively simple and effective technique for the formation of large
amount of small particles (nano-size) in the form of suspension.
2. Nanoparticle properties can be changed by selecting the laser parameter
and nature of liquid accordingly.
3. Nanoparticles formation is possible without adding surfactant in liquid
media.
Disadvantage
• Prolong time laser ablation leads to formation of high amount of
nanoparticles in the colloidal solution which block the laser path and also
laser energy is get absorbed by already formed nanoparticles instead of
target surface. This overall leads to reduction in ablation rate.
Application
1. Preparation of Al2O3 nanoparticles coating.
2. Preparation of silicon nanoparticles.
Ion sputtering
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• Sputtering is a process through which microscopic particles of a target
material get ejected from its surface after the bombardment of energetic
ions of gas or gaseous plasma. Momentum exchange between atoms and
ions of the element causes sputtering.
• There are several sputtering techniques such as DC diode sputtering, RF
radio sputtering, and magnetron sputtering are the most popular and widely
used sputtering processes.
• It is a widely used technology in modern-day engineering to produce fine
thin films of materials.
• Thin films are widely used across several industries such as
microelectronics (i.e. CPU processors, watches, batteries, cell phones,
iPod), solar panels, medical, oxidation resistance, and anti-reflective
coatings on cars, jewelry, mirrors, etc.
• Moreover, the sputtering process is also used for etching, analysis for
identification of the target material, and for space weathering.
• Sputtering processes are extremely useful across several industries such
as optical coatings, semiconductors, microelectronics, and many more.
Ion sputtering
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• Ion sputtering method includes vaporization of a solid through sputtering with a
beam of inert gas ions.
• Using magnetron sputtering of metal targets.
• The nanoparticles are formed and the mass nanostructured films are deposited
on the silicon substrates.
• The entire process is performed at relatively low pressures (1 mTorr).
• Sputter deposition is done in evacuated vacuum chamber where sputtering gas
is admitted and working pressure (eg. 0.05 and 0.1 mbar) is maintained.
• A very high voltage is introduced in to the target (cathode) and free electrons
are moved in spiral path using magnetic system where they collide with
sputtering gas (argon) atoms and leads to ionization of gas.
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Disadvantages
The nature sputtering gas (He, Ne, Ar, Kr, and Xe) can produce effect on
surface morphology, composition, texture, and the optical properties of the
nanocrystalline metal oxide films.
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Application
1. Synthesis of variety of nanomaterials on surface that employed for
catalysis process, photovoltaics, magnetism, memory, cluster-surface
interactions, hydrophobic coatings, and “nanoportals” for hydrogen storage.
2. For preparation of core-satellite Si–Ag and stable Pd-core MgO-shell
nanoparticles for the catalytic methanol oxidation reaction.
3. Heavy and complex ions such as peptides, proteins, protein assemblies,
organometallic complexes, metal clusters, and nanoparticles can be easily
placed on the substrates without altering their basic properties.
4. This method allows deposition of large molecules like large non-volatile
species that are not easy to deposit by traditional atomic and molecular
layer deposition techniques.
Bottom up methods
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• Nanoparticle synthesis using bottom up
approach is based on formation nanoparticles
from smaller molecules like joining of atoms,
molecules or small particles.
diacetylene dinitrile
Chemical vapor deposition method
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Disadvantages
1. Chances of chemical hazards because of toxic, corrosive, and explosive
precursor gases.
2. Multicomponent material deposition is difficult.
Application
1. Preferred method for the preparation of gas sensitive SnO2 nanorod
using aerosol assisted chemical vapor deposition.
2. Preparation of zirconia alumina nanopowder.
3. The chemical vapor deposition of large-area single-layer graphene on
metal such as Cu is performed using this technique and has wide
industrial applications.
Key differences between PVD and CVD
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Advantages
1. Simplest method.
2. Particle size and morphology is possible to control by
systematic monitoring of reaction parameters.
Applications
1. It is used for the synthesis of zinc peroxide (ZnO2)
nanostructures.
2. Preparation of NiO2 nanoparticles.
3. Thin metal films formation.
Chemical reduction
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Master title style
1. In chemical reduction method, ionic salt is reduced in an appropriate medium
in the presence of surfactant(substances lower the tension at the surface between
two liquids) using different reducing agents.
2. Reducing agents such as sodium borohydride is used in aqueous solution to
prepare metal nanoparticles.
Formed metal nanoparticles are capped by using trisodium citrate (TSC) or
sodium lauryl sulphate (SLS).
3. Sometimes stabilizing agent is used with reducing agent. The metal
nanoparticles stability in the dispersion was monitored by the analysis of
absorbance. Reducing agents such as sodium borohydrate (NaBH4), glucose,
ethylene glycol, ethanol, citrate of sodium, and hydrazine hydrate etc. are
used for silver nanoparticles synthesis.
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Advantages
Simplest method used for preparation of metal
nanoparticles.
Disadvantages
Several limitations associated with reducing agents such as
toxicity, expensive, poor reducing ability, high costs, and
impurities.
Applications
Preparation of copper nanoparticle using potassium
borohydrate as a reducing agent.
Hydrothermal
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• Hydrothermal method is based on
reaction of aqueous solution vapors
with solid material at high pressure
and temperature, and leads to
deposition of small particles.
• In this method cation, precipitate in
polymeric hydroxide form and
further these hydroxides get
dehydrated and accelerate
formation of metal oxide crystal
structure.
• The second metal cation formed is
beneficial for controlling particle
formation process by preventing
the formation of complex hydroxide
when base is added to metal salt
solution.
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Advantages
Desired size and shape nanoparticle can be prepared.
Well-crystallized powder can be formed.
Produce nanocrystal with high crystallinity.
Disadvantage
Processes are difficult to control.
Limitation of reliability and reproducibility
Applications
Suitable method for preparation of powders in the form of nanoparticle or
even in single crystal.
Solvothermal
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• Solvothermal method is used for the preparation of
nanophase in presence of water or other organic
chemicals like methanol, ethanol and polyol as a solvent.
• Reaction is produced in pressure vessel(Autoclaves) that
allows solvent (water and alcohol) heating above their
boiling point temperature.
• The kinetics of crystallization (crystal formation) can be
increased by the one to two orders of magnitude by
employing microwave assisted reactions (microwave
solvothermal).
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Advantages
1. Preparation of high quality crystallized monodispersed nanocrystals.
2. This method is more preferred for the preparation of narrow size
distribution of high degree of crystallization of nanocrystallites over
conventional oil bath heating.
Application
1. Synthesis of silver nanoparticles.
2. Rapid synthesis of nanostructures of Pt, Pd, Ag and Au using polyethylene
glycol or methanol as reducing agent under the microwave assisted
condition.
3. Wide application for the preparation of high quality crystallized
monodispersed nanocrystals of nitrites, metal oxide and new
semiconductor material.
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Gas phase methods - Spray pyrolysis
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Pyrolysis procedure for nanoparticle
preparation:
•Prepare a precursor solution. This can be
done by dissolving a suitable metal salt
(e.g., acetate, nitrate, chloride) in a solvent
(e.g., water, ethanol).
•Atomize the precursor solution. This can
be done using a nebulizer, ultrasonic
atomizer, or other atomization technique.
•Introduce the atomized precursor
solution into a hot reactor. The reactor
temperature should be high enough to
decompose the precursor and vaporize the
solvent.
•Collect the nanoparticles. This can be
done using a filter, electrostatic
precipitator, or other collection technique.
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Advantages
• Relatively simple method.
• Low cost method.
• The particle size can be
controlled and reproducible.
Applications
• Synthesis of nano-metal oxide
and mixed metal oxide.
• Synthesis of ZnO nanoparticles
by using zinc acetate as metal
precursor.
• Preparation of TiO2 nanoparticle.
Flame pyrolysis
FormationClick to edit
of nanostructures Master
by means title
of direct spraying style
of liquid precursor into
flame is the working principle of flame pyrolysis method. This method allows
delivery of precursors, which do not have sufficiently high vapor pressure in the
form of vapor.
The gases (vapor-fed aerosol flame synthesis), liquid (flame-assisted spray
pyrolysis: FASP and flame spray pyrolysis: FSP) or solid precursor is exposed to the
flame and allowed to form nanoparticles.
Biological method/biomimetic
method/green
Click synthesis
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Procedure
1. Choose a biological source: This could be bacteria, fungi, plants,
or plant extracts.
2. Prepare the biological source: This may involve growing the
microorganisms, extracting the plant compounds, or purifying the
enzymes.
3. Mix the biological source with a solution of metal ions: This is
the solution that you want to synthesize nanoparticles from.
4. Incubate the mixture: This will allow the biological source to
reduce the metal ions and form nanoparticles.
5. Purify the nanoparticles: This may involve washing the
nanoparticles with water or another solvent, or using
centrifugation to separate the nanoparticles from the rest of
the mixture.
Biological method
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Advantages of biological nanoparticle synthesis
•Cost-effective
•Eco-friendly
•Easy to scale up for large-scale production
•Does not involve the use of high pressure, energy, temperature, or toxic
chemicals
Advantages
•Simple, fast and inexpensive method.
•Unique method that produces nanoparticles of
controlled size and morphology.
•Major advantage is that the nanoparticles get
directly attached to the substrate.
Applications
•Synthesis of nanoparticles, nanowire, and
nanorods.
•Nanomaterial production such as nanowires of Au,
Co, Ni, and Pt.
Microwave assisted nanoparticles
preparation
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Nowadays microwave techniques are more
proffered over thermal heating for the
preparation nanoparticles.
• Microwave frequency of range
300 MHz to 300 GHz is applied that
leads to orientation of polar molecule
such as H2O with the electric field.
• The re-orientation of dipolar molecules
with an alternating electric field causes
molecular friction and loss of energy in
the form of heat.
• Recently this technique was
successfully implemented for the
preparation of silver nanoparticles
where silver nitrate solution is
irradiated with carboxymethyl
chitosan, which acts as reducing agent
and a stabilizer.
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Advantages
• Highly effective technology for nanoparticle preparation.
• Simple, rapid volumetric heating and the consequent dramatic increase in
reaction rate.
• Homogenous heating throughout the process can speed up the reaction
rate by the orders of magnitude compared with conventional heating.
Disadvantages
Shorter crystallization time and homogeneous nucleation because of
uniform heat of microwave oven.
Applications
• Useful technique in various fields of chemistry and materials science.
• Widely used for several plant-based extracts to prepare various metal
nanoparticles.
Ultra sound technique
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Ultrasound is a type of sound wave with a frequency higher than the range of human hearing
(above 20 kHz). Ultrasonic waves can be used to generate cavitation bubbles in liquids, which
are tiny bubbles that rapidly collapse and create high temperatures and pressures. This
process can be used to break down large particles into nanoparticles, or to promote the
formation of nanoparticles from smaller molecules.
Ultrasound-assisted synthesis of
nanomaterials has a number of
advantages over traditional
methods.
Additionally, ultrasound-assisted
synthesis is often more energy-
efficient and environmentally
friendly than traditional methods.
Ultra sound technique
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Advantages
• It is an ecofriendly, green, fast and easy method of
nanostructures synthesis.
• Successfully employed for less volatile organic liquids.
• By modifying reaction conditions several forms of nanostructures
of metals, oxides, sulfides and carbides can be prepared.
• For reduction of noble metal salts during nanostructure formation
reducing agent is not required, reaction rate is generally fast and
very tiny metal particles are produced.
Disadvantage
The rate of sonochemical reduction completely depends on
ultrasonic frequency.
Ultra sound technique
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Applications
• It is used to produce unusual nanostructured inorganic
materials such as carbonyl compounds (Fe(CO)5,
Co(CO)3NO, Mo(CO)6, and W(CO)6).
• Nanostructure material preparation from volatile
organometallic compounds.
Nanolithography
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Nanolithography is a process used to create structures on the
nanometer scale. It is used in a variety of industries, including
semiconductor manufacturing, MEMS/NEMS devices, and drug
delivery.
MEMS (Microelectromechanical Systems) and NEMS (Nanoelectromechanical
Systems) are devices that integrate mechanical and electrical components on
very small scales. While MEMS operate at the microscale (millionths of a
meter), NEMS function at the nanoscale (billionths of a meter). These devices
combine mechanical motion with electronic signals for advanced sensing,
actuation, and control.
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Nanolithography involves transferring a pattern from a "mask" or
template onto a material, typically using light, electrons, or other
energy sources.
• The process typically consists of:
1. Coating the Surface: A light-sensitive
material called a photoresist is applied to
the surface.
2. Patterning: The surface is exposed to light,
electrons, or another energy source to
create a specific pattern in the photoresist.
3. Etching: The unwanted material is
removed to reveal the pattern on the
surface.
4. Finalization: The patterned surface is
further processed, such as by depositing or
removing materials.
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Optical beam lithography:
Optical beam lithography uses light to expose the photoresist. The
wavelength of the light determines the minimum feature size that
can be created.
Electron beam lithography:
Electron beam lithography uses a focused beam of electrons to
expose the photoresist. This technique can create smaller features
than optical beam lithography, but it is slower and more expensive.
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Example:
1. To create a transistor, the following steps would be taken:
2. A photoresist is applied to a silicon wafer.
3. A mask with the pattern of the transistor is placed over the
photoresist and exposed to UV light.
4. The photoresist is developed, removing the exposed areas.
5. The silicon wafer is etched, transferring the pattern of the
transistor to the silicon.
6. The remaining photoresist is removed.
Challenges in nanophotonics
1. One of the main challenges in nanophotonics is the fabrication of
nanostructures with the desired optical properties.
2. Another challenge is the integration of nanophotonic devices into
existing optical systems. This can be difficult because
nanophotonic devices often operate at a different wavelength
range than traditional optical components.
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Future prospects of nanophotonics
For example,
1. Nanophotonic devices could be used to develop new types of
optical communication systems that are faster and more
efficient than current systems.
❑ Electronics:
1. Nano Transistors
2. Nano Diodes
Thank you