Overview of Nanomaterials

And their Applications

Prof. AJAYAN VINU

Global Innovation Chair Professor and Director
Global Innovative Center for Advanced Nanomaterials (GICAN)
School of Engineering, Faculty of Engineering and Built Environment,
Email: ajayan.vinu@newcastle.edu.au or vinu.ajayan@gmail.com

Date: 11th of January 2023, IIT Bombay, India

 Nanostructures in Nature and Biological Systems
Nanostructures in Lotus Leaf and Butterfly Wings

Application of nanomaterials in ancient times

Wootz Steel
(~500 BC)

~300 BC
Lycurgus Cup
Very strong
Scattering of Scattering of
High stability light by large light by “gold
because of the “silver nanoparticles
Fe3C nanowires nanostructures nanoparticles” with different
Carbon nanotubes sizes”
Tamil Nadu, India
Source: RSC, ACS and Elsevier publishing; Britishmuseum; Reibold et al. Nature Materials, 2006
 What is Nanoscale?
Fullerene – C60
Nanomaterial
Electron
Microscope

2.2 cm
~10 times
smaller
22 cm or 0.22 m 0.71 nm
0.71 X 10-9 m
Size of soccer ball
~0.3 billion times
smaller

Discovered in 1985; Nobel Prize in Chemistry 1996

Prof. R. Curl, Prof. H. Kroto, and Prof. R. Smalley

Nanoscale Materials: Materials of which a single unit is sized

in the range “1 to 100 nm” (10-9 m to 10-7 m) – Norio Taniguchi in 1974
 Nanomaterials – close view
❑ Nano = 10-9 m in size
❑ Nanomaterials : Materials with size of smaller than 100 nm in at
least one dimension (0.1 nm ~ 100 nm)
❑ 1 nm  3-5 atoms lined up in a row
❑ Human hair  ~ 80 m = ~ 80,000 nm : almost five orders of
magnitude

1m 10 cm 1 cm 100 m 10 m

1 nm 10 nm 100 nm 1 m

Types: Carbons, Metals, Ceramics (Metal oxides/hydroxide/sulfides, etc.)

Polymeric materials, or Composite materials
 Classification of Nanomaterials
Depending on their dimension (D)

(a) 0D Spheres and clusters (b) 1 D Nanofibers, Nanowires & Nanorods

CNT

C60 Ag Nanorod
Keggin Cluster
[XM12O40]n−, where X is the
heteroatom (P5+, Si4+, or B3+)
Carbon Nanofiber
(c) 2D Nanofilms, nanoplates and networks
Au Nanoplate
Graphene (d) 3D Nanomaterials

LDH

1 m 1 m

NanoDiamond Octahedral Cu2O

 Types of Nanomaterials

Nanoparticles

A. Geim

Nanotubes
Discovery of Graphene K. Novoselov
Nobel Prize in 2010
Prof. A. Geim and Prof. K. Novoselov

Nanorods

2D nanomaterials

Nanocrystals
 Nanoscale effects on properties
Properties Impact on their functions
Catalytic Better catalytic efficiency due to higher surface to volume ratio

Electrical Increased electrical conductivity in ceramics and magnetic

nanocomposites, increased resistance in metals

Magnetic Increased magnetic coercivity up to a critical grain size,

supermagnetic behaviour
Mechanical Improved hardness and toughness of metals and alloys,
ductility and superplasticity of ceramic
Optical Spectral shift of optical absorption and fluorescence
properties, increased quantum efficiency of semiconductor
crystals
Medical Increased selectivity, hollow spheres for specific drug
transportation and controlled release
Biological Increased permeability through biological barriers, improved
biocompatibility.
 Properties

Melting Point Bandgap

The melting point decreases The band gap increases with

dramatically as the particle size reducing the size of the
gets below 5 nm particles

Chem. Mater. 2018, 30, 3952−3962

 Properties
Surface area World record of surface area..!!!!
The total surface area (or) the number of
surface atom increases with reducing size
of the particles

The researchers showed that the

theoretical upper limit for MOF
surface area is 14600 m2/g (one
gram of material would cover 2.7
American football fields), possibly
higher…….!!!!!!!!

RSC Advances 3(40):18202-18215 http://www.kurzweilai.net

 Properties
Optical Properties

• Blue shift of the band gap as well as appearance of discrete sub-bands

corresponding to quantization along the direction of confinement occurs as a result
of quantum confinement.

• As the dimensions of the confinement increases, band gap decreases resulting in

the shift of interband transition to a higher wavelength and finally approach to that of
the bulk value for a large dimension.
doi.org/10.1016/j.jare.2010.02.002
• Controlling the size will help the fabrication of a number of devices.
 Tuning the Optical Properties

• The transverse band is insensitive to the size changes, the longitudinal band is red shifted
largely from the visible to near-infrared region with increasing aspect ratios (Length/Width),
causing the color changes from blue to red (shape effect)

• Gold shell coated on silica spheres – hybridization affects the bandgap of the materials
doi.org/10.1016/j.jare.2010.02.002
 Properties
Electrical Properties
Electrical properties of nanomaterials are sensitive to their structure.

Graphene is a zero band gap

semiconductor and Carbon
nanotubes can be metals or
semiconductors with varying energy gaps
depending on the diameter and helicity of
the tubes.
 Synthetic Scheme of Nanomaterials
Two key approaches: Top-Down and Bottom-Up

Clusters
Atoms
Nanomaterials
or
Bulk Material (0D, 1D, 2D & 3D
Molecules
Nanocrystals)

Top-Down Bottom Up
▪ Ball milling ▪ Sol-Gel Process
▪ Exfoliation ▪ Sputtering Process
▪ Focused Ion Beam (FIB) ▪ Chemical Vapor
Lithography Deposition
▪ Anodizing method (AAO) ▪ Laser atomic ablation
▪ Electrospinning
Examples of Top-Down Approach

http://www.kashima-coat.com/global/aluminum/anodized-aluminum.html

Heinz et al. “Focused Ion Beam Lithography”

J. Mater. Chem. A, 2015, 3, 11700–11715

Examples of Bottom-Up Approach
Large Area Graphene

Chen et al. Synthetic Metals 210 (2015) 95–108

Electrospun CNT-Carbon Nanofiber Composite

Hou et al., Chem. Mater.,17 (2005) 973

Z. Sun et al. Sensors and Actuators B 183 (2013) 297–302

Gold nanoparticles
 Comparison

❑ Top-Down Methods

➢ Begin with a pattern generated on a larger scale, then

reduced to nanoscale.
➢ By nature, aren’t cheap and quick to manufacture
➢ Slow and not suitable for large scale production.

❑ Bottom-up Methods
➢ start with atoms or molecules and build up to nanostructures
➢ Fabrication is much less expensive
Bottom-up approach

17
 Bottom-up approach
Chemical Precipitation
Nanoparticles of metals, alloys, oxides,
etc. are prepared in aqueous or organic
solutions.

Pros: Can produce large quantities

and Cost efficient

Cons: Random distribution of particle

size which is normally undesirable in
nanoengineering applications.

Parameters that control particlegrowth

1. Concentration of precursors
2. Concentration of reducingagent
3. Additives: Stabilizer (surfactants)
4. Temperature of the reaction
 Sol-Gel Method
This is based on the transition of a
system from a liquid solution “Sol”
into a gelatinous network “Gel”
phase.

It is a long established industrial

process, cost effective and
versatile.

It is possible to create at low

temperature ceramic or glass
materials in a wide variety of
forms.

It has been developed in last years for:

• Advanced nanomaterials and coatings
• Oxide nanoparticles
• Composite Nano-powders synthesis
• Access to organic inorganic materials
 Hydrothermal Method
Autoclaves
▪ Hydrothermal dissolution/precipitation reaction –the
basic mechanism for the hydrothermal formation of
ceramic oxideparticles
▪ Typical reacting temperature100~374oC
▪ Pressure range0~15MPa
▪ The product is crystalline anhydrous ceramic
powderswith controlled particles size, controlled
stoichiometry, and controlled particle shape.
(Calcination is not necessary)
▪ Starting precursor can be inexpensive oxides,
hydroxides, chlorides andnitrates.

Growth
 Sputtering and Thermal Evaporation
Consists of a vapour source inside a vacuum chamber containing and inert gas
(usually Ar or He). The vapour source can be an evaporation boat or a sputtering
target.
Supersaturation is achieved by resistive heating, radio-frequency, heating, sputtering,
electron beam heating, laser/plasma heating, or ion sputtering above the vapour
source and nanoparticles are formed
Pros: It is very versatile,
easy to perform and to
analyze the particles,
produces high quantity, high
purity materials, naturally
produces films and coatings
Cons: costly, it is difficult to
produce as large a variety of
materials as compared to
the one feasible by chemical
means
 Bottom-Up Approach (1)
Self Assembly of Monomer (Sol-Gel Process)

1/Concentration of monomer
http://www.mtl.kyoto-u.ac.jp/english/laboratory/nanoscopic/nanoscopic.htm Top-down and bottom-up approach to self-assemble multifunctional
porous films, Daniela Marongiu

The Colloidal Domain Where Physics, Chemistry, Biology and Technology Meet; Evans, D. F., Wennerström, H.
 Bottom-Up Approach (1)
Nanocasting method

Highly ordered 3D mesoporous nanostructures

Synthesis of MCNs by hard templating approach. (A) Preparation of the MCN-1 using SBA-15 with EDA and CTC, (B)
Schematic wall structure of the MCN-1, and (C) HR-TEM and HR-SEM images of the MCN-1 samples prepared at different EDA to
CTC weight ratios.
A. Vinu, K. Ariga, T. Mori, T. Nakanishi, S. Hishita, D. Golberg, Y. Bando, Adv. Mater., 2005, 17, 1648.
A. Vinu, Adv. Funct. Mater., 2008, 18, 816.
 Bottom-Up Approach (1)
Reduction & Nucleation & Selective Crystal Growth
Reduction & nucleation Coalescence of nuclei
> 200 ms
< 200 ms

M+

M+ M+

Precursor Nuclei
Nanoparticles

Lemon grass extract Polyol reduction with Hydrothermal in PVP

as reducing agent Polyvinylpyrrolidone (PVP) and I- ion
Polte et al., ACS Nano, 2010, 4, 1076; Zheng et al, J. Am. Chem. Soc., 2006, 128, 6550; Shankar et al., Nat. Mater., 2004, 3, 482; Sun et al.
Science, 2002, 298, 2176; Huang et al., J. Am. Chem. Soc., 2009, 131, 4602
 Bottom-Up Approach (1)
Bimetallic nanocrystal with different morphology

Au@Ag

Pd@Au Pd/Au@Au Cube

nanorod

Polavarapu et al, CrystEngComm, 2015, 17, 37272

 Bottom-Up Approach (1)
Self Assembly of Exfoliated Nanosheets
 Bottom-Up Approach (1)
Self assembled nanosheets through electrostatic interaction

Pore size:
2 nm < d
< 50 nm
Negatively Electrostatic
surface charged interaction
2D NS

Mesoporous 3D nanostructure

BET surface area

99 m2/g
Capacitance
209 F/g

Y. R. Lee et al., Chem. Eur. J. 2013, 18, 2263. Principle of supercapacitor

 Bottom-Up Approach (2)
Vapor Deposition
Physical Vapor Deposition (PVD) Chemical Vapor Deposition (CVD)
❑ Physically transport material from a ❑ Deposition can also take place due to a
condensed phase source to a substrate. chemical reaction between some reactants
❑ The substrate is somehow emitted from on the substrate.
the source (evaporation, sputtering). ❑ In this case reactant gases (precursors) are
❑ No chemical reactions are assumed. pumped in to a reaction chamber (reactor).
In fact, they are generally unwanted. ❑ Under the right conditions (T, P), they
If there are chemical reactions (as in undergo a reaction at the substrate.
reactive sputtering) they are simple ❑ One of the products of the reaction gets
reactions with no by-products. deposited on the substrate.
❑ The critical parameters are physical ❑ The by-products are pumped out.
(temperature, pressure, applied voltage , ❑ The key parameters are chemical (reaction
etc.) rates, gas transport, diffusion).
 Bottom-Up Approach (2)
Physical Vapor Deposition (PVD)
ZnO nanowire via PVD Au nanowire via PVD followed by
Electrodeposition

Kong et al., Appl. Phys. Lett., 2001, 78, 407 Cross et al., Langmuir 2007, 23, 10372
 Chemical Vapor Deposition
• The substrate is exposed to one or more volatile precursors
which react and decompose on the substrate surface to
produce the desired deposit.
• Volatile by-products are also produced, which are removed
by gas flow through the reaction chamber.

Types of CVD systems:

• Thermal (800C-1000C) and rapid
thermal CVD
• Atmospheric pressure CVD
• Atomic layer CVD
• Low-pressure CVD
• Metal-organic CVD based metal
organic precursors.
• Ultra high vacuum CVD
• Laser CVD
• Plasma CVD
• Photoinitiated CVD
• Aerosol/Liquid injection CVD
Bottom-Up Approach (2)
Chemical Vapor Deposition (CVD)

Fundamental CVD Processes

1. Convective and diffusive
transport of reactants to the
reaction zone
2. Gas phase reactions
3. Transport of reactants to the
substrate surface.
4. Chemical and physical
adsorption
5. Surface reactions leading to film
formation
6. Desorption of volatile
byproducts
7. Convective and diffusive
transport of by-products away
from the reaction zone
 Chemical Vapor Deposition (CVD)
Example of CVD
Catalytic growth of single-crystal monolayer graphene via CVD

Precursor: EtOH, C2H2, etc

Catalyst: Au, Cu, etc.

Lee et al., Science 344 (2014) 286–289.

 Bottom-Up Approach (2)
Selective Growth of Carbon Nanotube via CVD
RF
Scheme of an inductively coupled plasma reactor
Power Supplywith independent RF power CVD

Delzeit et al., J. Appl. Phys. Teo et al., Appl. Phys. Lett.

2002, 91, 6027 2001, 79, 1534.
 Bottom-Up Approach (3)
Laser Ablation Process

Silicon Carbon Surface oxidized Ni

Target (disk)

Kim et al., KONA Poder & Particle Jounal, 2017, 34, 80

 Bottom-Up Approach (4)
Electrospun Ceramic Nanofiber
Nanofiber is continuously spun formed by the electrostatic repulsion between surface
charges of injector and collector from a viscoelastic fluid.
A typical electrospinning process for
ceramic nanofiber
(i) Preparation of a stable colloidal suspension
(the sol) from a sol−gel precursor, a
polymer, and a solvent
(ii) Fabrication of composite nanofibers by
electrospinning;
(iii) Generation of ceramic nanofibers through
selective removal of the organic component
by calcination

Anatase TiO2 Nanofiber

( Xue et al., Acc. Chem. Res. 2017, 50, 1976)
 Bottom-Up Approach (4)
Electrospun Titania Hollow Nanofiber
Direct fabrication of nanofibers with a hollow structure

Electrospinning

Selective removal of liquid core

(calcination or solvent extraction)

The spinneret : two capillaries needle

ex) an inner flow : heavy mineral oil
an outer flow : PVP solution containing Ti(OiPr)4

Li et al., Nano Lett. 2004, 4, 933 TiO2 Hollow Nanofiber

Top-down approach 37
 Top Down approach

Lithography
At the moment, the most used top-down approach is photolithography. It has been
used for a while to manufacture computer chips and produce structures smaller than
100 nm.
Typically, an oxidized silicon
(Si) wafer is coated with a 1µm
thick photoresist layer.
After exposure to ultraviolet
(UV) light, the photoresist
undergoes a photochemical
reaction, which breaks down
the polymer by rupturing the
polymer chains.
Subsequently, when the wafer
is rinsed in a developing
solution, the exposed areas are
removed.
 Photolithography
Advantages
▪ Once the master template has been made, no special equipment is
required.
▪ Soft lithographic methods are capable of producing nanostructures in a
wide range of materials and can print or mold on curved as well as
planar surfaces

Disadvantages

▪ Nanostructures significantly smaller than 100 nm are difficult to

produce due to diffraction effects,
▪ Masks need to be perfectly aligned with the pattern on the wafer,
▪ Photolithographic tools are very costly, ranging in price from
tens to hundreds of millions of dollars.
 Electron-Beam Lithography
• Electron-beam lithography and X-ray
lithography techniques have been developed as
alternatives to photolithography.

• The pattern is written in a polymer film with a

beam of electrons. Since diffraction effects are
largely reduced due to the wavelength of
electrons, there is no blurring of features, and thus
the resolution is greatly improved.

• In the case of X-ray lithography, diffraction

effects are also minimized due to the short
wavelength of X-rays, but conventional lenses
are not capable of focusing X-rays and the
radiation damages most of the materials used
for masks and lenses.
 Top-Down Approach (3)
Photolithography

The E-beam is turned on/off and

directed in a prearranged pattern
over the surface of the resist. Copyright Stuart Lindsay (2008)
 Focused ion-beam (FIB) machining
• FIB machining offers the greatest
resolution, with the ability to make features
as small as 20 nm
• Gallium ions from a liquid metal ion source
is accelerated, filtered, and focused with
electromagnetic lenses to give a spot size
of 5–8 nm
• The high-energy ions blast atoms from
the surface, allowing simple cutting of
slots and channels or the creation of
more elaborate 3-D shapes.
• The precision is extraordinary.

Advantages SEM images of the FIB samples

• No radiation
• No scattering
• High precision
• Higher resolution
• Excellent precision
 Top-Down Approach (3)
Soft Lithography
“Soft” means no energetic Soft lithography:
particles (electron, ions) or • Low cost
radiation (UVs, X-ray) is • Molding, printing or transferring
involved. Instead, soft • Resolution usually not very high
elastomeric stamp is used. • Application in microfluidic, biomedical …
PDMS: poly(dimethyl-siloxane)

PDMS properties:
• Silicone elastomer
• Flexible and easy to mold
• Chemically inert
• Optically transparent
• Durable (reusable), low thermal
expansion
• Biocompatible
• Environmentally safe
• Best Resolution: 2-10 nm (for
hard PMDS)
 Top-Down Approach (3)
How to make nanopatterns with PDMS stamp

J. Mater. Chem. C 2016, 4, 3467-3476

ACS Appl. Mater. Interfaces 2016, 8, 25, 16368-16378
 Top-Down Approach (3)
Metal transfer assisted nanolithography: line-width reduction
Top-Down Approach (3)
Application of soft lithography
Lab on a chip

Application of lab on a chip: Health care sensor

 Summary

❑Top-down processing has been the dominant process in

synthesizing 0D/1D/2D/3D nanomaterials.

❑Newer technologies such as nanotubes and nanoporous

materials will require a bottom-up approach for
processing.

❑Bottom-up processing will become more and more

prevalent in synthesizing nanomaterials such as
nanoparticles, nanowires, nanotubes, nanosheets and
nanocrystals together with nanohybrid materials.
 Ball Milling

• Popular, simple, inexpensive and extremely

scalable material to synthesize all classes of
nanoparticles.

MECHANICAL ATTRITION MECHANISM is

used to obtain nanocrystalline structures from
either single phase powders or amorphous
materials.

• Can use either Zirconia balls or steel balls

or agate balls depending on the material to
be synthesized.

Working Principle: When the balls rotate

at a particular rpm, the necessary energy is
transferred to the powder which in turn
reduces the powder of coarse grain-sized
structure to ultrafine nano range particle.
 Top-Down Approach (1)
Mechanical Milling

Ball materials : Zirconia, Alumina, Stainless Steel, etc.

Parameters : Ball Milling Time & Power (spin speed)
 Top-Down Approach (1)
Mechanical Milling of ZnO Salah et al., Int. J. Nanomed. 2011, 6, 863.
0h 2h

10 h 20 h 50 h
 Top-Down Approach (1)
Mechanical Milling of Graphite Baek et al., Adv. Funct. Mater. 2015, 25, 6961.

graphite Graphene nanoplatelets

(a) Planetary ball‐mill machine; (b–d) schematic representation of the

mechanochemically driven physical cracking, and chemical reaction by ball‐milling
graphite in the presence of corresponding reactant(s) to produce edge‐selectively
functionalized graphene nanoplatelets (EFGnPs) with desired functional group(s).
 Top-Down Approach (2)
Exfoliation of Layered Materials to Nanosheets (NS)
Org. Intercalate precursor

Metal oxide
NS

Interlayer H2 evolution

Metal sulfide
NS

Osmotic Swelling

LDH NS
 Top-Down Approach (2)
Exfoliation of Layered Materials to Nanosheets

Oxidant Sonication
Reductant

Graphene

HF etching Sonication

MXene

H. Tang et al., Prog. Nat. Sci.: Mater. Int. 2018, 28, 133-147.
 Top-Down Approach (2)
Duality of exfoliated 2D nanosheet with bulk- and nano-properties

Schematic model of monolayer of MnO2

d < 1nm

Diverse compositions of inorganic nanosheets with versatile

functions - Tyndall effect

MnO2 [Mn1/3Co1/3Ni1/3]O2 CoO2 Zn-Cr-LDH Ni-Fe-LDH Fe-doped Ni-doped Co-doped

TiO2
titanate titanate titanate

Example of [Mn1/3Co1/3Ni1/3]O2 Nanosheet E. J. Oh et al., ACS Nano 2010, 4, 4437-4444.

exfoliation
Recent Advances in Nanoporous Materials
 Porous Materials and their Advantages
Classification of Porous Materials

Microporous <2nm Mesoporous Macroporous

Zeolites 2-50 nm > 50 nm
SBA-15
LTA

(100)
Silica gels

Intensity / (arb. Units)

MFI
KIT-6
FAU

(110)
(200)
EO20PO70EO20//

(210)

(300)
Butanol
2 4 6 8 10
EO20PO70EO20 Angle 2 / °
Active
Zeo-type EO PO70EO106 Charcoal
KIT-5 106

ALPO mesoporous
carbons
MOF

Well Ordered Porous Structure

Advantages of High Surface Area and Pore Volume
nanoporous materials Uniform Pore Size Distribution 56
High Thermal and Mechanical Stability
 Porous Materials and their Advantages
Porosity measurement
There are three parameters used as a measure of porosity; specific surface
area, specific pore volume or porosity, and pore size and its distribution.

Total surface area, m2

Specific Surface Area, m /g =2

Mass of the solid, g

Porosity, % =
Volume of pores
X 100
Volume of solid (including pores)

Pore size and

its distribution Specific Pore volume, cm3/g
Total pore volume, cm3
Porosity =
Mass of the solid, g
57
 Microporous materials
Microporous crystalline zeolite materials
Zeolites- ZSM-5 using SDA as template Zeolite beta synthesis by using
organic structure directing agent
(OSDA) free approach

Materials Research Bulletin, 2015, 65, 253-259

Nature, 2003, 425, 385

Microporous inorganic solids: Applications:

Zeolites Catalysts
Zeotypes Molecular sieves
(microporous aluminophosphates, Sorption
chlatrasils…) Ion exchange 58
 Microporous materials
Synthesis of Microporous Metal Organic Frameworks (MOFs)
MOF synthesis and new family of MOFs MOFs advantages:
➢ High specific surface areas
up to 3000 m2/g
➢ Highly crystalline nature
➢ Narrow pore sizes mainly in
the micropore region
➢ Enormous possibility for the
synthesis of vast number of
MOFs based on linkers

MOFs are built by linking inorganic parts (metal ions, clusters) using organic linkers
MOF world Applications

: Science, 2013, 341, 974; Chem. Soc. Rev.,

2014,43, 5867-5895
59
 Covalent organic frameworks (COFs)

a) Fluorescent TP-COF7. b) Fluorescent PPy-COF8. C) Fluorescent Py-Azine-

COF29. D) Fluorescent TPE-Ph-COF31. E) Conductive TTF-Ph-COF15–17. F)
Conductive HBC-COF
COFs advantages:
➢ High specific surface areas up to 2500 m2/g
➢ Metal free nature
➢ Highly crystalline nature
➢ Lot of possibilities depend on the different precursors 60
Nature Review Mater., 2016, 1, 1
 Idea and approach: Structural and morphological
modification of nanoporous carbons
Hard and soft templating approach – introducing ordered porous structure
Hard-Templating Approach

Soft-Templating Approach

Powder: Selective adsorption and separation 61

 New Strategy – Combining MW and HT

P-123 +H2O
+HCl

Cationic – Cetyltrimethylammonium Bromide Reaction time – short (from 72 h to 1 h)

Non-ionic Pluronic P123 EO20PO70EO20 High synt. temp. – Large pores and pore volume
62
Mesoporous materials (2-50 nm pore diameter)
Preparation of mesoporous materials via soft templating

➢ (A) Cooperative self-assembly; (B) Liquid-crystal templating processes for the preparation
mesoporous materials
➢ Pore dimensionality control: Making of 3D mesoporous silica

Chem. Rev., 2007, 107, 2822 63

 Mesoporous metal oxides
Preparation of mesoporous metal oxides via soft templating
approach
Ligand-assisted self- TEM images of a) CeO2, b) Co3O4, c) Cr2O3,
assembly approach d) CuO, e) Fe2O3, f) b-MnO2, g) Mn2O3, h)
Mn3O4, i) NiO

NPG Asia Materials, 2018, 10, 800–809 Catal. Lett., 2009, 64

Mesoporous thin films (2-50 nm pore diameter)
Mesoporous silica thin films via EISA process
Cooperative self-assembly of mesostructures via EISA process
for mesoporous materials

Chem. Rev., 2007, 107, 2822 65

Mesoporous thin films (2-50 nm pore diameter)
Mesoporous titania thin films via EISA process
Cooperative self-assembly of mesostructures via EISA process
for mesoporous materials

J. Mater. Chem. A, 2013, 1, 1591 66

 Mesoporous metals and bimetals
Preparation of mesoporous metals and bimetals via soft
templating approach
Lyotropic Liquid Crystals (LLCs) Mesoporous bimetallic and trimetallic spheres

Electrochemical micelle assembly

Adv. Mater., 2016, 28, 993–1010 67

 Mesoporous hollow spheres
Mesoporous materials with hollow structure
Soft templating method

selective etching strategy

68
Adv. Mater. 2010, 22, 4885–4889 and Adv. Mater. 2012, 24, 1504–1534
Mesoporous carbons (2-50 nm pore diameter)
Soft templating approach for mesoporous polymers and
carbons
Soft template assisted EISA procedure to prepare mesoporous polymers
and carbon frameworks

C-FDU-15

C-FDU-16

C-FDU-15:
Surface area: 968 m2 g-1
Pore volume: 0.56 cm3 g-1
C-FDU-16:
Surface area: 778 m2 g-1
Pore volume: 0.44 cm3 g-1

Adv. Mater. 2013, 25, 5129–5152 69

Mesoporous materials (2-50 nm pore diameter)
Nanocasting hard template approach

Chem. Soc. Rev., 2011, 40, 3854–3878 70

 Ordered mesoporous carbon
Nanocasting hard template approach for mesoporous carbon

Chem. Soc. Rev., 2011, 40, 3854–3878 71

MCN and its multiple properties and applications

Types of CN: Graphitic C3N4; α-C3N4, β-C3N4,

cubic and pseudo cubic CN

Synthesis: Can be synthesized by using

chemical or molecular precursors - nonporous
 Ordered mesoporous carbon nitride (MCN)
Nanocasting hard template approach for MCN

Gold supported MCN MCN nanoparticles

Chem. Soc. Rev., 2011, 40, 3854–3878 73

 Ordered mesoporous C3N4 (MCN)
Nanocasting hard template approach for mesoporous C3N4
Synthesis of 2D mesoporous C3N4 MCN C3N4 nanoparticles

Chem. Soc. Rev., 2017, 46, 72--101 74

Nitrogen enriched mesoporous carbon nitride
Nanocasting hard template approach for N rich MCN
Novel mesoporous C3N5 Diamino tetrazine based mesoporous C3N6

Angew. Chem. Int. Ed. 2017, 56, 8481 –8485 J. Mater. Chem. A, 2017, 5, 18183–18192 75
 Mesoporous metal nitrides
Reactive templating approach for mesoporous metal nitrides
Reactive templating approach for TiN

Mesoporous bimetal nitrides

Adv. Mater. 2009, 21, 4270–4274

Chem. Soc. Rev., 2017, 46, 72--101 76

 Mesoporous metal oxides
Hard templating approach for mesoporous metal oxide

Combined assembly by soft and hard template (CASH) method

Chem. Soc. Rev., 2014, 43, 313-344

77
 Mesoporous metal oxides
Mesoporous metal oxides properties prepared from
nanocasting hard template approach
Mesoporous CO3O4 templated Mesoporous Nb2O5 prepared from CASH method
from KIT-6

Mesoporous Cr2O3 templated

Mesoporous Co3O4 templated
from KIT-6
from SBA-16 and FDU-12

78
Chem. Soc. Rev., 2014, 43, 313-344
 Mesoporous metal chalcogenides
Hard templating approach for mesoporous WS2 and MoS2
Mesoporous MoS2 for
Li-ion batteries

Mesoporous MoS2:
BET surface area = 110 m2 g-1
Pore volume = 0.19 cm3 g-1

Mesoporous WS2:
BET surface area = 105 m2 g-1
Pore volume = 0.21 cm3 g-1

J. AM. CHEM. SOC. 2007, 129, 9522-9531 79

MMM, 2012, 151, 418–423
 Mesoporous metal chalcogenides
Hard templating approach for mesoporous metal
chalcogenides
Mesoporous CdS, ZnS and In2S3 CdS film CdTe film
Templated from SBA-15

Chem. Soc. Rev., 2011, 40, 3854–3878

Chemistry Letters, 2003, 32, 824 80
Nanoporous Soft Materials through Nanotemplating
Nanoporous Fullerenes Nanoporous Conducting Polymers

Nanoporous conducting
polymers with high surface
area

Nanoporous Biomolecules - Proteins

Vinu et al. Adv. Mater. 2017, 29, 1702295

Vinu et al. US Patent 2016; Nature Mater. 2018 Communicated

Advanced Nanostructures with a High Specific Surface Area
from Natural Resources
Natural Clay Nanotubes into High Surface Natural Biomass into High Surface
Area Porous Carbons or Nitrides Area Porous Carbons or Nitrides or
Carbides
Minotaur Exploration

(SA: 800 to 1400 m2/g)

(SA: 800 to 3900 m2/g)

 Mesoporous metal carbides
Templating approach for mesoporous metal carbides
Templating approach for mesoporous Mo2C Mesoporous WC

Applied Catalysis B: Environmental 147

ACS Appl. Energy Mater. 2018, 1, 736−743 (2014) 518– 525 83
 Advanced Carbon Nanostructures

Prof. AJAYAN VINU

Global Innovation Chair Professor and Director
Global Innovative Center for Advanced Nanomaterials (GICAN)
School of Engineering, Faculty of Engineering and Built Environment,
Email: ajayan.vinu@newcastle.edu.au or vinu.ajayan@gmail.com

Date: 4th of December 2018, GIAN, Mangalore University

 Carbon
• Carbon compounds form the basis of all known life on earth.
• Carbon has several allotropes and the most common allotropes of carbon
are graphite and diamond.
• Carbon atoms can form a wide range of structures due to its diverse
hybridisation states to covalently bond with other carbon atoms.
• Due to this distinct property, various carbon nanostructures can be formed
which can be used in various applications ranging from energy storage
and conversion to health.

Diamond Graphite
Electrical Insulator and Good conductor and
thermal Conductor thermal insulator
Periodic table
 Carbon Nanostructures
0D 1D 2D 3D

Fullerenes

Carbon Nanotube Graphene

Carbon like onions Graphite

Carbon nanofibers Multilayer Graphitic

Nanosheets
Carbon dots and
graphene quantum dots

Carbon Nanohorns Graphene

Nanodiamonds Nanoribbons Diamond
 Applications

• Water • Lead Pencils

Purification • Dry
Lubricants
Activated Graphite
Carbons

Graphene,
CNT Diamond

• Battery • Jewellery
• Supercapacitor • Cutting Tools
 Fullerenes
• Fullerenes are the purest form of carbon with different
number of hexagon and pentagon rings
• Unlike graphene, fullerenes have high thermal and
mechanical stability
• However the electrical conductivity and the surface
area of fullerenes are low
• Due to the unique structure of the fullerene, they are
considered as promising candidates for multifarious
applications
 Ordered Mesoporous fullerene C60
• Ordered mesoporous fullerene C60 was prepared by
our group for the first time

• High structural order and high surface area is

obtained for all the samples

• Highly crystalline nature of C60 is obtained

• TEM images shows highly ordered mesostructure

with clear lattice fringes TEM

XRD
Schematic of ordered mesoporous C60
Angew. Chem. 2018, 130, 578 –582
 Fullerene C60 nanorods
• Fullerene C60 nanorods were prepared by
(liquid-liquid interfacial precipitation) LLIP
method in ultra fast procedure of 5
seconds
• The prepared samples show hexagonal
close pack crystal structure
• The newly developed materials can be a
viable candidate for optoelectronic
applications

XRD of C60 nanorods and

pristine C60

LLIP synthesis of C60 nanorods

SEM and TEM of C60 nanorods
ACS Appl. Mater. Interfaces 2014, 6, 15597−15603
 C60 nanowhiskers
• C60 nanowhiskers were prepared by LLIP method
also with photo assisted preparation conditions

• The length of the nanowhiskers are found to be

controllable by varying the illumination conditions

Optical micrographs of C60

nanowhiskers

SEM images of C60 nanowhiskers by LLIP

Chemical Physics Letters 374 (2003) 279–285
 C60 nanoflowers using surfactants
• Different structure of C60 crystals were obtained by very
small amount (0.001-1.0%) of surfactant induced
synthesis strategy
• In the absence of surfactant , 1D C60 nanowhiskers
(nanorods) and C60 nanotubes are obtained. When
surfactants are incorporated into the system flowerlike
microcrystals consisting of C60 nanotubes are observed.
• Interestingly the C60 nanoflowers shows
photoluminescence properties SEM of C60 nanowhiskers

1.From diglycerol monolaurate 2. From cetyltrimethylammonium 3. From cetyltrimethylammonium

bromide chloride
Langmuir 2013, 29, 7195−7202
 C60 nanosheets
• Size controlled hexagonal C60
nanosheets were prepared by selecting
the proper solvent for the synthesis
condition

• These nanosheets can lead to

opportunities in various applications

SEM of C60 nanosheets at CCl4 and IPA

interface

XRD of C60 hexagonal TEM of C60 nanosheets from CCl4 and EtOH
nanosheets
J. AM. CHEM. SOC. 2007, 129, 13816-13817
 C60 nanostructures into nanorods
• Hexagonal, rhombi and mixed
polygonal structures were
obtained by LLIP method.

• Shape shifting of these

structures to nanorods (short
nanowhiskers) is demonstrated SEM and TEM from (a) TBA/
in this work toluene, (b) IPA/CCl4, and (c)
TBA/benzene interfaces

1. Hexagons 2.Rhombi 3.
Polygons
J. AM. CHEM. SOC. 2009, 131, 6372–6373
 Carbon Nanotubes
• Theoretical surface area of 50 to 1315 m2/g
• Unique tubular structure and High density of
mesopores
• Large accessibility of electrolyte ions
• Can be further enhanced by metal oxides, ACs and CPs
• Can be used in flexible energy storage systems
 CNT sponges
• CNT sponges were synthesized by CVD
process using ferrocene and 1,2-
dichlorobenzene as the catalyst precursor
and carbon source, respectively
• A small densified pellet floating on water
surface can quickly remove a spreading oil
film with an area up to 800 times that of the
sponge
Illustration of the sponge consisting of
CNT piles (black lines) as the skeleton and
open pores (void space)

TEM SEM CNT sponge bent to

arch-shape
Adv. Mater. 2010 , 22, 617–621
 MnO2 nanospheres/CNT/Conducting polymer composite

• MnO2/CNT/CP composite materials are

prepared as an electrode material for
supercapacitor exhibiting specific
capacitance as high as 427 F/g

• Also the cycling stability shows over 99%

of initial capacitance retained even after
1000 cycles

(A) TEM image of fFWNTs, (B) TEM image of direct mixing of MnO2 nanospheres with fFWNTs, and (C) TEM
and (D) SEM images of PEDOT-PSS dispersed MnO2 nanospheres in situ grown on fFWNTs
Nano Lett. 2010, 10, 2727–2733
 Coaxial MnO2/CNT array

• MnO2/CNT composites
were prepared for lithium
ion batteries and showed
improved performance
when compared to pure
CNT and pure MnO2

Single coaxial nanotube SEM image

XRD

Discharge capacity vs
cycle number SEM
Schematic of MnO2/CNT hybrid coaxial
nanotube Nano Lett., Vol. 9, No. 3, 2009
 Fe3O4 hollow nanospheres/CNT
• Fe3O4 hollow
nanospheres/CNT is
prepared via a one pot
solvothermal treatment
and showed dielectric
heating performance
under microwave
irradiation Magnetic decantation
TEM

Microwave pathway of Fe3O4/CNT SEM

composite
Materials Letters 235 (2019) 31–34
 Binder free LiCoO2/CNT for lithium ion batteries

• Ultrasonication and codeposition

technique is used for the preparation
electrode material (super aligned
CNT/LiCoO2 composite) for lithium
ion batteries

SEM of SACNT

SEM of SACNT/LiCoO2
a) the binder-free LiCoO 2 -SACNT cathode and b) the
classical LiCoO 2 -Super P cathode Adv. Mater. 2012, 24, 2294–2298
 Graphene
• Graphene was discovered by Novoselov and Geim with a micromechanical
exfoliation method in 2004
• Graphene are 2D flat monolayer of carbon atoms which function as exceptional
crystal and electronic properties
• Large theoretical surface area of 2630 m2/g
• Good electrical and thermal conductivity, Great mechanical strength
• Graphene based frameworks such as sponges, foams, hydrogels and aerogels are
emerging ultralight weight electrodes

Raman spectra of graphite and

graphene monolayers
Graphene wrapped up into 0D fullerenes, 1D
Solid State Communications 143 (2007) CNT or 3D graphites
47–57 Nature Materials volume 6, pages183–191 (2007)
 Preparation methods of Graphene

• CVD
• Plasma Etched CVD
Bottom Up • Graphitization
• Solvothermal
• Organic Synthesis
• Liquid exfoliation of graphite
• Thermal exfoliation and liquid
intercalation
Top Down • Electrochemical exfoliation
• Chemical reduction of GO
• Thermal reduction of GO
• Photothermal reduction of GO
Graphene nanosheets in Lithium ion batteries
• Graphene nanosheets were prepared
from graphite powders by chemical
exfoliation and used as an anode in
lithium ion batteries
• After 100 cycles, as much as 460
mAh/g was obtained showing much
better cycling stability compared to
graphite Charge discharge curves

Raman spectrum of graphene

FEG-SEM TEM
nanosheets and pristine graphite
powders(inset)
CARBON 47 (2009) 2049 – 2053
 Fe3O4/N-Graphene Aerogels
• Fe3O4/N-doped graphene
aerogels can be prepared
by a combined
hydrothermal, self assembly,
freeze drying process

• The prepared material is

tested for ORR and showed
better durability than Pt/C TEM of Fe3O4/N-GA

SEM of Fe3O4/N-GA

J. Am. Chem. Soc. 2012, 134, 9082−9085 Schematic of Fe3O4/N-graphene aerogel

 Graphene nanosheet/Fe3O4
• Graphene nanosheet/Fe3O4 composite material are
prepared by insitu reduction of iron hydroxide
between graphene nanosheets

• The GNS/Fe3O4 materials exhibited 700 mAhg-1 after

100 cycles for lithium ion batteries

TEM of GNS/Fe3O4

SEM of GNS/Fe3O4
Schematic of a Flexible Interleaved Structure
Chem. Mater., Vol. 22, No. 18, 2010 Consisting of GNSs and Fe3O4 Particles
 Graphene Sulphur composite
• Graphene sulphur composite materials were
prepared and used as cathode material for
lithium sulphur batteries with capacity as high as
~600 mAh/g for more than 100 cycles

SEM of graphene sulphur composite Graphene sulphur composite schematic

Nano Lett. 2011, 11, 2644–2647
 Graphene Mn3O4 hybrid
• Mn3O4 nanoparticles are grown on
reduced graphene oxide sheets
and applied as an anode material
for lithium ion batteries.
• Capacity as high as ~900 mAh/g
was obtained with good cycling
stability and rate capability
Capacity retention of Mn3O4 and
Mn3O4/reduced GO

Schematic two-step synthesis of Mn3O4/RGO

TEM images of Mn3O4/ RGO

J. AM. CHEM. SOC. 2010, 132, 13978–13980
 Graphene PANI composite
• Graphene PANI composites are
prepared as an electrode material for
supercapacitor

• These materials could produce

specific capacitance of 480 F/g at 0.1
A/g Polyaniline Graphene Reduced
Oxide Graphene

Polyaniline (PANI)
Graphene Oxide
nanofibers

Schematic of Graphene-PANI Composites

Chem. Mater. 2010, 22, 1392–1401
 Carbon Dots
• Carbon based quantum dots are new class of carbon nanomaterials
with size below 10 nm
• It was first prepared by the purification of single walled carbon
nanotubes by electrophoresis in 2004
• Due to its abundant and inexpensive nature, with properties such as
good solubility and strong luminescence, they are rising as new class
of materials for various applications

Biome Optro Sensor Catalys

dicine nics s is

Applications

Nano Research 2015, 8(2) 355–381

 Carbon Nanodots Preparation Methods

Synthetic Method Advantages Disadvantages

Chemical Ablation Most accessible, various Harsh conditions, drastic
sources processes, multiple steps,
poor control over sizes
Electrochemical Size and nanostructure are Few small molecule
Carbonization controllable, stable, one step precursors
Laser Ablation Rapid, effective, surface Low QY, poor control over
states tunable sizes, modification is needed
Microwave irradiation Rapid, scalable, cost effective, Poor control over sizes
eco-friendly
Hydrothermal/solvothermal Cost effective, eco-friendly, Poor control over sizes
treatment non toxic
Carbogenic dots using mesoporous silica as nanoreactors

• Mesoporous silica spheres were

used as nanoreactors to produce
hydrophilic carbogenic dots by
impregnation method

• The resultant material are low

toxic, photostable and
monodisperse (a)Plain sample (b)
Fluorescent under visible HRTEM
light

Chem. Commun., 2011, 47, 764–766

 Carbon dots using silica spheres as carriers

• Photoluminescent carbon quantum dots

with amorphous nature and 1.5 to 2.5 nm
size were obtained using silica and
surfactant as starting material with
quantum yield as high as 14.7% is obtained
HRTEM

Confocal microscopy images

of E. coli at different
wavelength
Angew. Chem. Int. Ed. 2009, 48, 4598 –4601
Amino functionalized fluorescent carbon dots
• Hydrothermal carbonization of
chitosan at 180⁰C was
performed to obtain amino
functionalized carbon dots with
low cytotoxicity

HRTEM AFM

(a) A confocal fluorescence microphotograph of cells labeled with the CNPs

(b) (b) A brightfield microphotograph of the cells. (c) An overlay image of (a) and (b).

Chem. Commun., 2012, 48, 380–382

Graphene quantum dots derived from carbon fibers

• Graphene quantum dots

prepared by exfoliation and
etching of carbon fibres with
controllable size, low toxicity and
excellent bio-compatibility

Fluorescent images of human breast cancer cell (a) phase contrast HRTEM
picture of cells. (b) Individual nucleus stained blue with 4′,6-diamidino-2-
phenylindole (DAPI). (c) Agglomerated green GQDs surrounding each
Nano Lett. 2012, 12,
nucleus. (d) The overlay high contrast image of nucleolus stained with
844−849
blue DAPI and GQDs (green) staining
 Advanced Porous Materials for Energy,
Environment and Healthcare Applications
Environment Rechargeable Battery Materials

Li+ Li+

Li+
C3N5
Li+ Li+
C3N6
Li+ Li+ C3N7
…

Highly ordered porous structure of CN

Li+
Na+,
K+ & Li+

Fighting Climate Change Li+

batter Li+

y
Energy
CO2 Capture and Conversion Materials
Advanced Porous
Materials
Carbon nitride,
carbon, fullerene,
metal oxide, metal
nitride, metal
sulphides, boron
carbon nitride, 2D
Next-generation Battery Materials materials and hybrid Hydrogen
materials
 Applications
Medicine
Diagnostics and Cancer therapy
The NanoFlares are designed to bind genetic targets in cancer cells, and generate
light when that particular genetic target is found

Nanoparticles, typically smaller than 100 nm, have been applied to medicine due
to their unique magnetic properties and sizes, comparable to the largest biological
molecules, such as enzymes, receptors, or antibodies, that enable diagnostic,
therapy as well as combined therapy and diagnostic (known as theranostics).
Nanoparticles with potential MRI-related medical applications comprise various
materials, such as metals (gold, silver, and cobalt) or metal oxides (Fe3O4, TiO2,
and SiO2)
doi.org/10.1016/j.sbsr.2016.08.002
Nanomaterials for Drug delivery system
Nanomaterials in carrier- based Drug delivery system

•The Scientific World Journal 2014(4):276260

 Nanomaterials for Energy storage
Carbon nanostructures as electrode
Li-ion Batteries materials for Batteries

High capacity of 1200mAh/g for Nano CoO

anchored graphene composite

doi.org/10.1557/mrc.2017.30
 Limitation of Lithium Ion Batteries
Conventional Lithium Ion Battery (LIB)

Central technology to delivering significant Limitation?

advances in a wide range of industries, from
electric vehicles to renewable power! - Insufficient specific capacity
(conventional graphite anode
electrode: 372 mAh/g)
- Insufficient energy density
- Insufficient longevity
- Very limited lithium resource
- Safety concern

We need battery breakthroughs in terms of material aspect

 Na-ion Batteries

Battery-grade salts of sodium are

cheap and abundant, much more so
than those of lithium. This makes them
a cost-effective alternative especially
for applications where weight and
energy density are of minor importance
such as grid energy
storage for renewable energy sources
such as wind- and solar power

Chem. Soc. Rev., 2017, 46, 3529-3614

 Nanoporous Carbons from Biomass
SA: 3535 m2/g SA: 2473 m2/g
SA: 3617 m2/g SA: 3106 m2/g SA: 2230 m2/g
PV: 1.9 cm3/g PV: 0.72 cm3/g
PV: 2.16 cm3/g PV: 1.62 PV: 0.0.96 cm3/g
97% mesopores PS: 0.7 nm
PS: 2.7-3.1 nm
7wt% oxygen

39.8 Two tonnes

Almond Casein
of CO2 per
ton of the
adsorbent –
The best CO2
adsorbent
 Molecular machines

The Nobel Prize in Chemistry 2016 is

awarded to Jean-Pierre Sauvage, Sir J.
Fraser Stoddart and Bernard L.
Feringa for their design and production
of molecular machines. They have
developed molecules with
controllable movements, which can
perform a task when energy is added
 Solar Cells

Solar cells

DSSC converted in to window panels at EPFL

Solar cells