Nanotechnology in Catalysis

(CH-456)

Instructor: Dr. Santanu Paria

Phone: 2262 (O), 3262 (R), 9437684864 (M)

E-mail: santanuparia@yahoo.com, sparia@nitrkl.ac.in
Website: http://geocities.com/santanuparia

Department of Chemical Engineering

NIT Rourkela
 Syllabus
•Fundamentals understanding of catalysis at nano-scale: Catalysis in the field of
nanoscience and nano-technology, molecular ingredients of catalytic activity and
selectivity
•Synthesis, properties, stability and characterization of nano-particles: Wet chemical
synthesis, preparation and properties of iron, platinum, gold, cadmium, silver, copper
and nickel nano-particles
•Synthesis and properties of composite nano-particles and coated nano-particles: Wet
chemical synthesis
•Applications of nano-particles in catalysis in quasi homogeneous reactions,
heterogeneous reactions, fuel cell catalysis, selective hydrogenations, benzene
hydrogenation, environmental clean-up technology
•Nano-particle characterization instruments
 Syllabus
•Introduction
Definition
History
What makes the nanoscale so different from the other length scales by
considering the underpinning science (i.e. nanoscience) and some key examples
of nanotechnology. Main engineering activities of design, manufacture and
testing in a nanotechnology context.
•Methods of synthesis of nanometerials fabrication- “Top-down” vs. “bottom-
up” approaches.
•Focus on different nanomaterials: Carbon nanotubes, Inorganic nanowires-,
Organic molecules for electronics, Biological and bio-inspired materials,
Metallic nanomaterials, Different shape nanomaterials.
•Applications of nano-particles in emerging fields like catalysis, biological and other
systems.
•Characterization of nano particles by Atomic Force Microscopy, Scanning
Tunneling Microscopy, Transmission Electron Microscopy, Scanning Electron
Microscopy.
 Interdisciplinary Area
Physics
Chemistry
Electrical
Engg.

Comp. Sci.

Chemical
Engg. Nanotechnology
Mat. Sci.

Bio
Technol.
Metallurgy,
Pharmaceutical
Medical
Civil
 Institutions which have started courses in
nanotechnology
•Jawaharlal Nehru Center for Advanced Scientific Research,
Bangalore
•Indian Institute of Science, Bangalore
•National Physical Laboratory, Delhi
•Solid State Physics Laboratory, Delhi
•National Chemical Laboratory, Pune
•Central Scientific Instruments Organization, Chandigarh;
•Defence Materials Store Research & Development Organizations,
Kanpur
•Indian Institutes of Technology at Kanpur, Chennai, Guwahati,
Delhi and Mumbai.
 Introduction
What is nanoscience and technology??
The prefix “nano” originates from the Greek word for dwarf, and thus refers to
something small. As a prefix for a unit of time or length, it means one billionth of that
unit.
• Technology development at the atomic, molecular, or macromolecular range of
approximately 1-100 nanometers to create and use structures, devices.
•Nanotechnology is the understanding and control of matter at dimensions of roughly
1-100 nanometers, where unique phenomena enable novel applications.
•Nanoscience involves research to discover new behaviors and properties of materials
with dimensions at the nano scale, which ranges roughly from 1 to 100 nm.
History:
Richard Feynman was the first scientist to suggest that devices and materials could
someday be fabricated to atomic specifications: “The principles of physics, as far as I
can see, do not speak against the possibility of maneuvering things atom by atom.”
1960’ s: Richard Feynman
First concept of Nanotechnology: A talk given by physicist Richard Feynman at an
American Physical Society meeting at Caltech on December 29, 1959, “There's Plenty
of Room at the Bottom”. The talk was first published in the February 1960 issue of
Caltech's Engineering and Science.
 Introduction
1970’ s: Norio Taniguchi
The term “nanotechnology” was defined by Tokyo Science University Professor
Norio Taniguchi in a 1974 paper: N. Taniguchi, “On the Basic Concept of 'Nano-
Technology”, Proc. Intl. Conf. Prod. Eng. Tokyo, Part II, Japan Society of
Precision Engineering, 1974.
He mentioned: “Nano-technology mainly consists of the processing of, separation,
consolidation, and deformation of materials by one atom or by one molecule.”

1980’s: K. Eric Drexler

The basic idea of this definition was explored more by Dr. K. Eric Drexler. He
received PhD from MIT in 1991. Dr. Drexler serves as Chief Technical Advisor to
Nanorex, a company developing design software for structural DNA
nanotechnologies. He promoted the technological significance of nano-scale
phenomena and devices through speeches and the books Engines of Creation: The
Coming Era of Nanotechnology (1986) on molecular nanotechnology and
Nanosystems: Molecular Machinery, Manufacturing, and Computation (1992), and
so the term acquired its current sense. The second book which received the
Association of American Publishers award for Best Computer Science Book of
1992.
 The Scope
•The scope and application of nanotechnology is tremendous. According to the
scientists, 21st century would be the nanotechnology century. It is estimated that
nanotechnology would revolutionize every area, be it medicine, aerospace,
engineering, various industrial and technological areas, health or any other field.
•The technology is ‘favorite of all’ kind of technological arena due to its
application in almost every field, from medicine to fabrics.
•Nanobiotechnology can make tiny medical devices and sensors with fantastic use,
targeting a drug to a single malignant cell, creating sensors in the form of biochip
etc.
Nanotechnology has many more applications. Nano- coatings are transparent,
scratch- resistant and dirt repellent. Thus, it is estimated that there will be no
sector of industry which will not use nanotechnology in future.

“Nanotechnology has given us the tools...to play with the ultimate toy box of
nature — atoms and molecules. Everything is made from it...The possibilities to
create new things appear limitless.”
– Horst Stormer
Lucent Technologies and Columbia University,
Physics Nobel Prize Winner (1998)
 What’s so special about the nanoscale?
•The short answer is materials can have different properties at the nanoscale. e. g.
•Types of properties as their size is changed

Optical (e.g. color, transparency)

Electrical (e.g. conductivity)

Physical (e.g. hardness, melting point)

Chemical (e.g. reactivity, reaction rates)
•Nanoscale material also have far larger surface area than similar volume of larger
scale materials, meaning that more surface is available for interactions with the
other materials around them.
Examples:
COAL and DIAMONDS, sand and computer chips, cancer and healthy tissue:
throughout history, variations in the arrangement of atoms have distinguished the
cheap from the precious, the diseased from the healthy.
Arranged one way, atoms make up soil, air, and water; arranged another, they make up ripe
strawberries. Arranged one way, they make up homes and fresh air; arranged another, they
make up ash and smoke.
Our ability to arrange atoms lies at the foundation of technology. We take pride in our
technology, with our lifesaving drugs and desktop computers.
But the laws of nature leave PLENTY OF ROOM for progress, and the pressures of world
competition are even now pushing us forward. For better or for worse, the greatest
technological breakthrough in history is still to come
 The nanoscale in perspective
How small in one nanometer?
By definition one nanometer is one billionth of a meter (10-9m) but that’s a hard
concept to most of us to grasp.
Units
• Meter (m)
• Millimeter (mm) = 10-3m
• Micrometer (µµm) = 10-6m
• Nanometer (nm) = 10-9m
• Picometer (pm) = 10-12m
• Femtometer (fm) = 10-15 m
The nanoscale in perspective
 Intensive versus Extensive properties
Physical properties of matter are categorized as either Intensive or Extensive:

Intensive or bulk properties that do not depend on the amount of the matter
present.
•Color
•Odor
•Luster - How shiny a substance is.
•Malleability - The ability of a substance to be beaten into thin sheets.
•Ductility - The ability of a substance to be drawn into thin wires.
•Conductivity - The ability of a substance to allow the flow of energy or electricity.
•Hardness - How easily a substance can be scratched.
•Melting/Freezing Point
•Boiling Point
•Density - The mass of a substance divided by its volume
By contrast, an extensive property of a system does depend on the system size or the
amount of material in the system.
•Mass, length, volume, entropy, enthalpy, energy, electrical resistance, texture, heat
etc.
 Intensive versus Extensive properties

The fact that properties change with scale is not consistent with the traditional
concept of “intensive properties” which are defined as independent of the
amount of material (e.g. melting point, conductivity, malleability, etc.).
However, that definition only applies on the macroscale.
As the size of the material gets smaller and approaches the nanoscale, some of
those intensive properties do, indeed, change. Therefore, properties can no
longer be categorized without qualification as those that do change (extensive)
and those that do not (intensive) because all properties can change depending
on scale.
 Change in property in nanoscale
The color of gold is a classic example of how properties can change based on the size
of the particles. When we have an aggregation of gold atoms bonded together in a
solid with a diameter of about 12 nanometers, we can observe the color of the
nanoparticles by looking at a bunch of them suspended in water. If the atoms are in
the right bonding arrangement, we see that the gold nanoparticles (12-13 nm)
appear red, not gold-colored. If we add a bunch more atoms in the right
arrangement, we see the particles look purple.
Why?
Gold nanoparticles abosorb light at different wavelenghts
depending on their diameter due to their size dependent
surface plasmon resonance frequency. This fact is responisble
for the beutiful colors gold nanoparticles show when exposed
to light. This is true for many materials when the particles
have a size that is less than 100 nanometers in at least one
dimension.
What is color?

For many objects, their color depends on which wavelengths of

light are reflected and absorbed by the object’s atoms or molecules.
For example, a red object is good at reflecting red wavelengths of
visible light (and good at absorbing all of the other wavelengths of
visible light).
Scientists think that a totally different process happens when light
interacts with nanoparticles. It’s called surface plasmonics.
 So why does the gold look red?

When nanoscale-sized clusters of gold atoms are hit with light

energy, the surface atom’s free electrons begin to “slosh” back
and forth and create electrons waves called surface plasmons..
Then, these electron waves
produce light energy which is
released. The color of the light
produced depends on the size
and shape of the nanocluster.
The excitation of surface plasmons by light is denoted as a surface plasmon resonance
(SPR) for planar surfaces.
Surface plasmons, also referred to in the literature as surface plasma polaritons, are
fluctuations in the electron density at the boundary of two materials
 Nanotechnology in painting or jewelry

Dispersions of discrete gold nanoparticles in The same gold nanoparticles shown are
transparent media viewed in transmitted light pictured here in reflected light.

Particle size of gold (spherical): Silver (spherical): Shape dependence

2-5 nm = Yellow color 40 nm = Blue
10-20 nm = Red 100 nm = Yellow 100 nm prism = red
> 20 nm = Purple
 Applications
The Cup of Lycurgus (from 4th century A.D., currently housed in the British
Museum). This extraordinary cup is the only complete example of a very
special type of glass, known as dichroic, which changes colour when held up to
the light.
This is an example of gold nanoparticles being used in glass from ancient
history. When light shines through the glass, the charasteristicred color of
gold nanoparticlescan be seen.

Transmitted light
Reflected light
(Red and violet)
(Green)

http://www.britishmuseum.org/explore/highlights/highlight_objects/pe_mla/t/the_lycurgus_cup.aspx
 Applications of different nanoparticle for
making color
Gold ruby glass is a silicate glass containing well-dispersed nanometre
size gold metal particles imparting the glass its distinctive red color.
Gold ruby glass is mainly used for making household glassware.

Cu-glass
Mn-glass
Cr-glass

Co-glass
Ni-glass
 Applications
Optical Properties Example: Zinc Oxide (ZnO)

•Large ZnO particles

Block UV light

Scatter visible light

Appear white
•Nanosized ZnO particles

Block UV light
Nanoscale ZnO

So small compared to the wavelength of visible “Traditional” ZnO sunscreen is clear
light that they don’t scatter it sunscreen is white

Appear clear