Introduction to Chemistry of

Nanomaterials
 The Study of Chemistry
The Molecular Perspective of Chemistry
• Matter is the physical material of the universe.
• Matter is made up of relatively few elements.
• On the microscopic level, matter consists of
atoms and molecules.
• Atoms combine to form molecules.
• As we see, molecules may consist of the same
type of atoms or different types of atoms.
Molecular Perspective of
Chemistry
(Space filling models)
How to
understand
structures
Space filling
Wire frame
Ball and stick
 Why dimensions matter?
Nanomaterials – particles of nanometer size
Nano-scale materials often have very different
properties from bulk materials
e.g. color and reactivity

•30nm particle has 5% of atoms on the surface

•10nm particle has 20% of atoms on the surface

•3nm iron particle has 50% of atoms on the surface

 What is nanotechnology?

Ability to understand, create, and use structures, devices

and systems that have fundamentally new properties and
functions because of their nanoscale structure
Ability to image, measure, model, and manipulate matter
on the nanoscale to exploit those properties and functions
Ability to integrate those properties and functions into
systems spanning from nano- to macro-scopic scales
Research and technology development aimed to
understand and control matter at dimensions of
approximately 1 - 100 nanometer – the nanoscale
Moore’s Law - one motivation for nanotechnology
 Size-Dependent Properties

Even on macro scale properties of material can depend on

the size of the object treated.

For example,
(1) Dissolving powder vs. dissolving large chunks

(2) Starting fire with a timber log vs. using kindling

 Size-Dependent Properties

Powder has larger surface area than a chunk of the same

material exposed to the liquid, which does the
dissolution

Splints made from a log have much larger surface area

than the log from which they came – hence large
surface exposure to air (oxygen) needed for
combustion.
Size-Dependent Properties
At the nanometer scale, properties become dramatically
size-dependent.
For example,
(1) Thermal properties – melting temperature
(2) Mechanical properties – adhesion, capillary forces
(3) Optical properties – absorption and scattering of light
(4) Electrical properties – tunneling current
(5) Magnetic properties – superparamagnetic effect
New properties enable new applications
An electronic device with a nanotube
1. What could be the purpose of this device?
2. What methodology has to be mastered?
3. What (if anything) is wrong with this picture?
"Lately the prefix trend has been shrinking. During the
1980s, 'mini-' gave way to 'micro-,' which has yielded to
'nano-.' In the new millennium, companies such as
Nanometrics, Nanogen and NanoPierce Technologies
have all embraced the prefix, despite complaints their
products were hardly nano-scale (a billionth of a meter
or smaller). Even Eddie Bauer sells stain-resistant
nano-pants. (They're available in 'extra-large' for the
retailer's not-so-nano customers.)“

(Alex Boese, "Electrocybertronics." Smithsonian, March

2008)
Melting Temperature
Nanocrystal size decreases…
surface energy increases…
…melting point decreases

e.g., 3 nm CdSe nanocrystal melts at 700 K

compared to bulk CdSe at 1678 K
The melting point of gold particles decreases dramatically as
the particle size gets below 5 nm

Source: Nanoscale Materials in Chemistry, Wiley, 2001

Electrical Properties: Tunneling current
At the nanometer scale, electrical insulators
begin to block current flow.

The current increases exponentially as the

thickness of the insulator is decreased.

Certain phenomena occur only when characteristic dimensions reach the

nanometer scale
e.g., quantum tunneling effects:When you put a voltage across an
insulator, then the current is given by U=IR. When the insulator
becomes small (less than 100 nm) the current is much higher by
orders of magnitude than predicted due to tunneling
Historical Use of Nanoparticles: Stained
Glass

The Lycugus Cup. This cup is made of dichroic glass that has colloidal gold
and silver nano-scale particles in the glass. When held up to the light, the
ordinarily green cup (from the silver particles) shows up as red due to the gold
nanoparticles in the glass. More information, and the original images are
available from The British Museum.
 What is nanotechnology?

Ability to understand, create, and use structures, devices

and systems that have fundamentally new properties and
functions because of their nanoscale structure
Ability to image, measure, model, and manipulate matter
on the nanoscale to exploit those properties and functions
Ability to integrate those properties and functions into
systems spanning from nano- to macro-scopic scales
Research and technology development aimed to
understand and control matter at dimensions of
approximately 1 - 100 nanometer – the nanoscale
Why is nanotechnology unique?
Surface effects are very important: surface to volume
ratio is extremely large
Think of water flowing through your garden hose -
the fluid right near the wall acts very differently than the
rest of the fluid. This has a negligible effect on the water
coming out of the hose end.
When the garden hose shrinks to nanoscale dimensions -
all of the fluid is “near the wall”, and the laws that predict
how much fluid comes out as a function of pressure no
longer apply.
 Why is nanotechnology unique?
For materials with more than one atom, not only can the
arrangement of atoms at the surface be different, but the
composition can be different.
Say we have the compound AB-
Overall, we have equal amounts of A and B, but it is possible
that at the surface we have more A than B.
In conventional materials, this surface enhancement of A
does not affect the bulk properties, since the amount of
material at the surface is miniscule.
In nanomaterials, this surface enhancement not only affects
the “surface” properties, but it also affects the “bulk”
properties since there is much more B in the bulk, since the
amount of material at the surface is significant.
Unique properties of the material when the
size goes down
•Quantum size effects result in unique mechanical, electronic,
photonic, and magnetic properties of nanoscale materials

•Chemical reactivity of nanoscale materials greatly different

from more macroscopic form, e.g., gold

•Vastly increased surface area per unit mass, e.g., upwards of

1000 m2 per gram

•New chemical forms of common chemical elements, e.g.,

fullerenes, nanotubes of carbon, titanium oxide, zinc oxide,
other layered compounds
Atoms and molecules are generally less than a nm and we study
them in chemistry. Condensed matter physics deals with solids
with infinite array of bound atoms. Nanoscience deals with the
in-between meso-world
• Quantum chemistry does not apply (although fundamental
laws hold) and the systems are not large enough for classical laws
of physics
• Size-dependent properties
• Surface to volume ratio
- A 3 nm iron particle has 50% atoms on the surface
- A 10 nm particle 20% on the surface
- A 30 nm particle only 5% on the surface
SURFACE vs. VOLUME

Source: Nanoscale Materials in Chemistry, Ed. K.J. Klabunde, Wiley, 2001

Many existing technologies already depend on nanoscale materials
and processes
- photography, catalysts are “old” examples
- developed empirically decades ago

• In existing technologies using nanomaterials/processes, role

of nanoscale phenomena not understood until recently;
serendipitous discoveries
- with understanding comes opportunities for improvement

• Ability to design more complex systems in the future is ahead

- designer material that is hard and strong but low weight
- self-healing materials
 Various Nanomaterials and
Nanotechnologies
• Nanocrystalline materials • Molecular electronics
• Nanoparticles • Quantum dots
• Nanocapsules • NEMS, Nanofluidics
• Nanoporous materials • Nanophotonics, Nano-optics
• Nanofibers • Nanomagnetics
• Nanowires • Nanofabrication
• Fullerenes • Nanolithography
• Nanotubes • Nanomanufacturing
• Nanosprings • Nanomedicine
• Nanobelts • Nano-bio
• Dendrimers
 NANOSCALE PROPERTIES
• Size-dependent properties
color, specific heat, melting point, conductivity…..

• I-U of a single nanoparticle (Electrochemistry)

• Adsorption
- principles
- some examples

• Nanomaterial reinforcement in composites

- multifunctionality
- self-healing
SOME CONCEPTS AND DEFINITONS
• Cluster
- A collection of units (atoms or reactive molecules) of up to
about 50 units
• Colloids
- A stable liquid phase containing particles in the 1-1000 nm
range. A colloid particle is one such 1-1000 nm particle.
• Nanoparticle
- A solid particle in the 1-100 nm range that could be
noncrystalline, an aggregate of crystallites or a single
crystallite
• Nanocrystal
- A solid particle that is a single crystal in the nanometer range
• For semiconductors such as ZnO, CdS, and Si, the bandgap
changes with size of the particle
- Bandgap is the energy needed to promote an electron
from the valence band to the conduction band
- When the bandgaps lie in the visible spectrum, a change
in bandgap with size means a change in color

• For magnetic materials such as Fe, Co, Ni, Fe3O4, etc., magnetic
properties are size dependent
- The ‘coercive force’ (or magnetic memory) needed to
reverse an internal magnetic field within the particle is
size dependent
- The strength of a particle’s internal magnetic field can be
size dependent
 COLOR
• In a classical sense, color is caused by the partial absorption of
light by electrons in matter, resulting in the visibility of the
complementary part of the light
• On most smooth metal surfaces, light is totally reflected by the
high density of electrons, hence no color, just a mirror-like
appearance.
• Small particles absorb, leading to some color. This is a size
dependent property.
Example: Gold, which readily forms nanoparticles but is not
easily oxidized, exhibits different colors depending on particle
size.
- Gold colloids have been used to color glasses since early
days of glass making. Ruby-glass contains finely dispersed
gold-colloids.
- Silver and copper also give attractive colors
Surface Adsorption
• Adsorption is like absorption except the adsorbed material is held near the surface
rather than inside

• In bulk solids, all molecules are surrounded by and bound to neighboring atoms
and the forces are in balance. Surface atoms are bound only on one side, leaving
unbalanced atomic and molecular forces on the surface. These forces attract gases
and molecules  Van der Waals force,  physical adsorption or physisorption

• At high temperatures, unbalanced surface forces may be satisfied by electron

sharing or valence bonding with gas atoms  chemical adsorption or
chemisorption
- Basis for heterogeneous catalysis (key to production of fertilizers,
pharmaceuticals, synthetic fibers, solvents, surfactants, gasoline, other
fuels, automobile catalytic converters…)
- High specific surface area (area per unit mass)
• Physisorption of gases by solids increases with decreasing T and with increasing P
• Weak interaction forces; low heats of adsorption
< 80 kJ/mol; physisorption does not affect the
structure or texture of the absorbent
• Desorption takes place as conditions are reversed
• Mostly, testing is done at LN2 temperature
(77.5 K at 1 atm.). Plot of gas adsorbed as
volume Va at 0° C and 1 atm (STP) vs. P/Po
(Po is vapor pressure) is called adsorption
isotherm.
 Nanomaterial reinforcement
in composites
• Processing them into various matrices follow earlier composite
developments such as
- Polymer compounding
- Producing filled polymers
- Assembly of laminate composites
- Polymerizing rigid rod polymers

• Purpose
- Replace existing materials where properties can be superior
- Applications where traditionally composites were not a
candidate
• Nanotechnology provides new opportunities for radical changes
in composite functionality

• Major benefit is to reach percolation threshold at low volumes

(< 1%) when mixing nanoparticles in a host matrix

• Functionalities can be added when we control the orientation

of the nanoscale reinforcement.
 Some fundamental science issues
1. What novel quantum properties will be enabled by nanostructures (at room
temperature)?

2. How different from bulk behavior?

3. What are the surface reconstructions and rearrangements of atoms in

nanocrystals?

4. Can carbon nanotubes of specified length and helicity be synthesized as

pure species? Heterojunctions in 1-D?

5. What new insights can we gain about polymer, biological…systems from the
capability to examine single-molecule properties?

6. How can one use parallel self-assembly techniques to control relative

arrangements of nanoscale components according to predesigned
sequence?

7. Are there processes leading to economic preparation of nanostructures with

control of size, shape, etc., for applications?
Carbon structures
 Graphite:
black, opaque, lusterous, slippery,
conducts electricity

 Diamond:
colourless, clear, lusterous, high
m.p., does not conduct electricity

 Buckminster
fullerene:
Black solid, deep red solution in
petrol
 Forms of material
DIAMOND - GRAPHITE
 Forms of material
CARBON - GRAPHITE
 Nanotubes – How big?
Nanotubes are being
developed for use in
computer technology.

These tubes are:

1-2nm diameter
100mm long
 Types of nanotubes

Semiconductor:
It is a chiral nanotube - “twists” along its length.

Conductor (metallic):
Straight nanotubes
[Only conducts electricity under specific conditions]
Nanotubes & Fullerene derivatives
 Fullerenes
They are spheres of only carbon atoms and are also
allotropes of carbon

One example is the

Buckminsterfullerene (Buckyball)
It has a formula C60
It is a black solid
Dissolves in petrol to make a
red solution
Free moving electrons so conducts
electricity
Fullerenes
Fullerenes
 Fullerenes: Uses
They can cage other molecules

In the future this may be used to

deliver drugs in small amounts for
slow release.
E.g. Cancer treatment
 Nanotubes Uses
 Biological: drug delivery, trap dangerous substances,
immobilization of enzymes, DNA transfection

 Paints: improving strength & conductivity

 Actuators: changing electrical energy into mechanical

energy e.g. robotics

 Electronics: semiconductors, diodes.

 Chemical industry: catalysts e.g. zeolites in

hydrocarbon cracking

 Excellent website: http://nanotechinkorea.free.fr/english/nanoco.php

A range of applications intended to
improve life quality and to provide novel
approaches to diagnostic and therapy,
based on suitably designed
nanostructures, nanoparticles or smart
molecular systems.
Currently, a number of research groups is
studying such topics, as witnessed also by
specifically devoted scientific journals.
 The Nobel Prize in Physics 2010

Awarded jointly to Andre Geim and

Konstantin Novoselov "for groundbreaking
experiments regarding the two-
dimensional material graphene"
University of Manchester, UK
 The Nobel Prize in Physics 2010
Graphene

Graphene is an atomic-scale honeycomb lattice made of carbon

atoms. [Photo: Alexander Alus www.nobelprize.org]
 Carbon nanotube – extremely strong

Theoretical tensile strength 300 Gpa

Highest reported 63 Gpa

Kevlar 2.7 GPa

steel piano wire 2.4 GPa
spider silk 1 GPa
diamond - up to 60 GPa

Single walled nanotube

How is the strength measured?

Theoretical calculation

Experiment

Atomic force microscopy

Min-Feng Yu, Oleg Lourie, Mark J.

Dyer, Katerina Moloni,
Thomas F. Kelly, Rodney S. Ruoff
Science Vol 287, 28 Jan. 2000)
Inserting nanotubes into a circuit

Single electron transistor

 Nanofabrication
Top-down: Chisel away material to make
nanoscale objects
Bottom-up: Assemble nanoscale objects out of
even smaller units (e.g., atoms and molecules)
Ultimate Goal: Dial in the properties that you want
by designing and building at the scale of nature
(i.e., the nanoscale)
 Top-Down: Photolitography

Chisel away
material to make
nanoscale
objects
Bottom-Up: Molecular Self-Assembly

Assemble
nanoscale
objects out of
even smaller
units (e.g.,
atoms and
molecules)

Carbon Nanotube Synthesis

Acceptance of nanotechnology
 Application of nanochemistry

This discipline involves both new materials and new

principles, as powerful tools for an extremely
effective action against a range of diseases.
For example a physicochemical phenomenon called
Surface Plasmon Resonance is used to develope
a technology for drug discovery, antibody screening,
ligand fishing and therapeutics.
Application of nanochemistry

Futuristic kinds of nanorobots have been even

imagined, able not only to take care of our
health from inside our body, but also to
replicate themselves or to modify themselves
according to the specific problem to be solved.
Increasing funding initiatives are supporting
this fascinating and promising research field.
 Nanomedicine

Nanotechnology provides a wide range of new technologies for

developing customized solutions that optimize the delivery of
pharmaceutical products. Today, harmful side effects of
treatments such as chemotherapy are commonly a result of drug
delivery methods that don't pinpoint their intended target cells
accurately. Researchers at Harvard and MIT, however, have
been able to attach special RNA strands, measuring nearly
10 nm in diameter, to nano-particles, filling them with a
chemotherapy drug. These RNA strands are attracted to cancer
cells. When the nanoparticle encounters a cancer cell, it adheres
to it, and releases the drug into the cancer cell. This directed
method of drug delivery has great potential for treating cancer
patients while avoiding negative effects (commonly associated
with improper drug delivery)
 Nanorobotics

Nanorobotics is the emerging technology field creating machines

or robots whose components are at or close to the scale of
a nanometer (10−9 meters). More specifically, nanorobotics refers to
the nanotechnology engineering discipline of designing and
building nanorobots, with devices ranging in size from 0.1–10 micrometers and
constructed of nanoscale or molecular components.[ The
names nanobots, nanoids, nanites, nanomachines or nanomites have also
been used to describe these devices currently under research and development.
Diode:
The nanotube is used here to connect two
electrodes (yellow) on a silicon dioxide base (green)
[Diodes allow a current to travel in one direction only]

Superconductors or Insulators:
 NANOTUBES
Nanotubes are made by joining fullerenes together

Properties
 Hexagons curled into a
tube shape
 Very strong
 Conducts electricity
 Small with a large surface
area
 Can be separated from
liquid products for re-use
Uses
 Reinforce Graphite in
tennis racquets
 Semi conductors in electric
circuits in modern
computers and electric
circuits
 Industrial catalysts
Drug Delivery – ‘Buckydrugs’
‘Cages’ made of Buckminster fullerene
structures can be used to carry drugs
 Bacteria can be used to carry drugs, DNA or
sensors attached to nanoparticles into cells for
treatment, gene therapy or diagnosis.
Replacing Antibiotics