Engineering Chemistry – CS stream Module-3 : Green energy and Advanced engineering materials

NANOMATERIALS :
• Nanomaterials have one of its dimensions in the range of 1- 100 nm
For example chinese used gold nanoparticles as an inorganic dye into their ceramic porcelains more
than thousand year ago.
• Nanomaterials are promising because at nanoscale, its physical and chemical properties differ
significantly from its bulk structured materials.
For instance, bulk silver is non-toxic whereas silver nanoparticles can kill viruses upon contact.
• Properties like electrical conductivity, colour and strength change when the nanoscale is reached.
• It is already having a significant commercial impact, which will assuredly increase in the future.

Applications of Nanomaterials in Real life

• The range of commercial products available today is very broad, including stain-resistant and wrinkle
free textiles, cosmetics, sunscreens, electronics, paints and varnishes etc.
• Nanoscale titanium dioxide for instance is finding application in cosmetics, sunblock cleans, and
self-cleaning windows, and nanoscale silica is being used as filler in a range of products, including
cosmetics and dental fillings.

[Link] for more applications of nanomaterials

Size dependent properties of nanomaterials (Surface area, Electrical, and Optical

properties)

1. Surface Area

• When a bulk material is subdivided into individual nanomaterials, the total volume remains the same,
but the collective surface area is enormously increased.
• Nanomaterials have a large proportion of atoms existing at the surface.
• Properties like catalytic activity gas adsorption and chemical reactivity depend on the surface area.
• Therefore nanomaterials can show specific surface related properties that are not observed in bulk
materials.
Example:
Bulk gold is catalytically inactive, but gold nanoparticles are catalytically very active for selective redox
reaction.
 Engineering Chemistry – CS stream Module-3 : Green energy and Advanced engineering materials

2. Electrical Properties :

• Some metals which are good conductor in bulk become semiconductor

or insulator as their size is decreased to nano level.
• The reason is that the electronic bands in bulk material are continuous
due to overlapping of orbitals of billions of atoms.
• In Nanomaterials very few atoms or molecules are present and so the
electronic bands become separate and separation between different
electronic states varies with the size of nanomaterial.

3. Optical properties :

The optical properties of nanomaterials differ significantly from bulk materials due to their small size
and quantum effects. In nanomaterials, the interaction of light with electrons is influenced by quantum
confinement, leading to unique phenomena like size-dependent color and enhanced fluorescence. As
particle size decreases, energy levels become discrete, affecting how light is absorbed, emitted, and
scattered.
For example, gold nanoparticles can appear red, purple, or blue depending on their size, unlike bulk gold,
which is yellow. This color change occurs due to localized surface plasmon resonance (LSPR), where
the electrons on the nanoparticle surface oscillate in response to light. Nanomaterials are widely used in
applications like bio-imaging, sensors, and display technologies, where their unique optical properties
offer advantages over traditional materials.

Synthesis of nanoparticles :

1. Sol-Gel method
Sol-gel method of synthesizing nanomaterials is very popular amongst chemists and is widely employed
to prepare oxide nanomaterials.

The sol-gel process can be characterized by a series of distinct steps.

a. Preparation of sol
A stable colloidal solution called sol is prepared. (The sol is a liquid suspension of solid particles
ranging in size from 1nm to 1 micron). It is prepared by hydrolysis and partial condensation of
precursors such as metal alkoxide.
 Engineering Chemistry – CS stream Module-3 : Green energy and Advanced engineering materials

b. Conversion of Sol to Gel

Further condensation of sol into a three-dimensional network produce a gel material.

c. Aging of the Gel

Polycondensation reaction continue until the gel transforms into a solid mass accompanied by contraction of
the gel networks and expulsion of solvent from gel pores. The aging process of gels can exceed 7 days.

d. Drying of Gel
Water and other volatile liquid are removed from the gel network. If isolated by thermal evaporation, the
resulting monolith is termed a Xerogel. If the solvent (such as water) is extracted under-critical or near
super critical conditions, the product is an aerogel.

e. Dehydration - To stabilize the gel against any rehydration the surface-bound M-OH groups are
removed by calcining(heating) the monolith at temperature up to 800 C. 0

Example : Fabrication of zinc oxide (ZnO) nanoparticles by sol-gel method employing zinc acetate and
aluminium nitrate as precursors. The Aluminium nitrate was dissolved in zinc acetate dropwise followed
by centrifuging, drying and calcination at 200 ℃ yielding zinc oxide nanoparticles.
 Engineering Chemistry – CS stream Module-3 : Green energy and Advanced engineering materials

Advantages Sol-gel method

• Low temperature route (below 200 C) 0

• Uniform particle size distribution

• Can easily shape materials into complex geometries in gel state
• Simple, effective method to produce high quality coating
• High chemical reactivity of precursors due to process in solution phase

2. Co-precipitation method
• Preparation of nanoparticles can be achieved by careful precipitation of the substance from its
solution.
• In this process, acid or base is added to the precursor solution to adjust the pH to the desired level.
• Then a precipitating agent is added to it to initiate nucleus formation. The nucleus formed grows into
particles and gets precipitated. The precipitate is filtered, washed, air dried and calcined to obtain
nanoparticles.

For example:
Precipitation of Zinc oxide nanoparticles is carried out from Zinc acetate precursor solution by adding
precipitating agent and reducing agent Urea. Alkalinity was maintained by NaOH. Zn ions first react
2+

with base in presence of urea to form white precipitate called zinc hydroxide. After reaction completed
the reaction mixture was subjected to centrifuge and residue was dried and finally subjected to calcination
process where we can get fine white crystalline powder of ZnO nano particles.
 Engineering Chemistry – CS stream Module-3 : Green energy and Advanced engineering materials

Nanoscale materials : Fullerenes, Carbon nanotubes and graphene

1. Fullerene
• Fullerene is any molecule in the form of a hollow sphere, ellipsoid or tubular structure composed
entirely of carbon. They are commonly referred to as “Buckyballs” – named after Buckminster

Fuller
• It is a cage like molecules composed of 60 carbon atoms joined together by single and double
bonds to form a hollow sphere with 12 pentagonal and 20 hexagonal faces.

Properties of Fullerene
1. Unique Molecular Structure: Fullerenes have a spherical, cage-like structure (e.g., C60 or 'buckyball'),
giving them stability and symmetry.
2. High Electrical Conductivity: Fullerenes can conduct electricity and even exhibit superconductivity
when doped with certain metals.
3. Thermal Stability: Fullerenes are thermally stable and can withstand high temperatures without
decomposing.
4. Strong Antioxidant Properties: They can react with free radicals, making them effective antioxidants.
5. Solubility: Fullerenes are generally insoluble in water but dissolve in organic solvents, which makes
them versatile for different applications.
6. Photophysical Properties: They exhibit unique photoluminescence, fluorescence, and
photoconductivity, useful in optical applications.
7. Chemical Functionalization: Their structure allows for easy functionalization, enabling diverse
applications in various fields.

Applications of Fullerene
1. Medicine: Used in drug delivery systems, fullerene derivatives help target drugs to specific cells,
improving treatment efficacy.
2. Antioxidant in Skincare: Due to their antioxidant properties, fullerenes are added to skincare products
to help neutralize free radicals.
3. Electronics: Fullerenes are used in organic photovoltaics, as they help in electron transport in solar
cells, improving their efficiency.
4. Superconductors: When doped with alkali metals, fullerenes exhibit superconductivity, offering
potential in advanced materials and energy applications.
5. Lubricants: Their spherical shape provides low friction, making them effective as lubricants in various
mechanical systems.
6. Water Purification: Fullerenes are used to remove contaminants from water due to their ability to bind
with organic molecules and some heavy metals.
7. Hydrogen Storage: They are studied for hydrogen storage applications as they can adsorb hydrogen
molecules, making them promising for energy storage solutions.
 Engineering Chemistry – CS stream Module-3 : Green energy and Advanced engineering materials

2. Carbon nanotubes
• Carbon Nanotubes is a 1-dimensional carbon allotrope having a cylindrical structure and a central
hollow core formed by rolling up of graphene sheets.

• Carbon nanotubes are extremely robust and difficult to break, but they are still light.
• Diameter of CNT is 1 – 50 nm and the length is in few micrometers.
• Carbon Nano-tube Aspect ratio (length/Width) is generally greater than 1000.

Properties CNT’S (carbon nanotubes)

1. CNT’s having outstanding high electrical property. (six times of copper)
2. CNT’S have the highest tensile strength of an any material known.
3. CNT’s has high chemical storage capacity.
4. Elasticity: They are highly flexible and can bend without breaking, which allows them to return
to their original shape after deformation.
5. Stiffness: They exhibit very high Young’s modulus, making them exceptionally stiff.
6. Functionalizability: The surfaces of CNTs can be modified with functional groups to make them
compatible with other materials
7. High Surface Area: CNTs have a large surface area, making them ideal for applications in
sensors, adsorbents, and catalysts.

Application of CNT’s (carbon nanotubes)

• Transistors: CNTs are used to make field-effect transistors (FETs) with high-speed performance,
potentially enabling smaller and more efficient electronic devices.
• Conductive Films: They serve as transparent conductive films in touch screens, displays, and solar
cells, replacing materials like indium tin oxide.
• Batteries: CNTs are added to lithium-ion and other batteries to increase the electrode surface area,
enhancing energy density, conductivity, and charge/discharge rates.
• Fuel Cells: CNTs are used in the electrodes of fuel cells, offering high catalytic activity and
conductivity.
• Structural Reinforcement: CNTs are added to polymers, metals, and ceramics to create lightweight,
strong composite materials for aerospace, automotive, and sports equipment.
• Drug Delivery: CNTs can be functionalized to carry drugs to targeted cells, allowing for precision
medicine applications and minimizing side effects.
• Water Filtration: Due to their high surface area and ability to adsorb contaminants, CNTs are used
in filters to remove impurities from water, including heavy metals and organic compounds.
• Chemical and Gas Sensors: CNTs are sensitive to changes in their environment, allowing them to
detect gases like ammonia, carbon dioxide, and others at low concentrations.
 Engineering Chemistry – CS stream Module-3 : Green energy and Advanced engineering materials
• Pressure and Strain Sensors: They respond to pressure changes, making them ideal for
use in wearable devices or systems that monitor mechanical stress.

3. Graphene
• Graphene is 2 dimensional crystalline allotrope of carbon consisting of single layer of carbon
atoms arranged in hexagonal lattice.

Applications of graphene :
Graphite and its derivate recently gained science and engineering awareness due to its numerous
applications. The discovery of graphene is rightly regarded as a milestone in the world of material
science; as can be seen in the worldwide attention, the material has received in the fields of electronics,
photonics, capacitors / supercapacitors, biosensing, etc.
Electronics - Graphene’s are used in electronic fabrications as initial materials. Electronic devices such
as graphene effect transistors (GFETs) and field effect transistors (FETs) are graphene-based. They are
widely used in the manufacturing of electronic devices like light-emitting diodes (LEDs) and solar cells.
Energy storage - Reduced graphene oxide nanocomposites have a high surface area and good
conductivity, which suited them for use in supercapacitors and lithium-ion batteries with good energy
storage capacity. GO-based supercapacitors and lithium-ion batteries possess high-energy storage
capacity, long life span, and good cycle stability.
Water purification - Graphene-based thin film possesses the quality of filtering dirty and salty water.
These films are non-heavy and can be easily produced on a large scale.
Purification of water can be done by graphene, which removes 95% of heavy metal ions.
In 2011, some group of researchers employed the principle of reverse osmosis using Graphene oxide to
achieve desalination of water.
Sensors - Functionalized graphene has important applications as biological and chemical sensors.
Biomedical application - Graphite and its derivative like GO are widely used in the biomedical field as
a constituent in the drug delivery system.
Sound Transducers - Graphene has been predicted as a good candidate for the manufacturing of
electrostatic audio microphones and speakers due to their lightweight, which provides moderately good
frequency response.
Engineering Chemistry – CS stream Module-3 : Green energy and Advanced engineering materials
Engineering Chemistry – CS stream Module-3 : Green energy and Advanced engineering materials