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Chapter 1-1-Introduction to nanochemistry-P

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Chapter 1-1-Introduction to nanochemistry-P

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2

REFERENCES
NANOCHEMISTRY & APPLICATIONS [1] Tahir Awan, Almas Bashir, Aqsa Tehseen, 2020. Chemistry of Nanomaterials:
Fundamentals and Applications. Elsevier.
[2] C. N. R. Rao, A. Muller, A. K. Cheetham, 2004. The Chemistry of Nanomaterials: Synthesis,
Properties and Applications. Wiley-VCH.
CHAPTER 1: [3] Anatoliy Petrovych Shpak, Petr Petrovych Gorbyk, 2010. Nanomaterials and Supramolecular:
Structures Physics, Chemistry, and Applications. Springer.
INTRODUCTION TO NANOCHEMISTRY [4] Bharat Bhushan, Dan Luo, Scott R. Schricker, Wolfgang Sigmund, Stefan Zauscher, 2014,
Handbook of Nanomaterials Properties. Springer.
[5] Yury Gogotsi, 2017. Nanomaterials Handbook (2nd ed.). CRC Press.
[6] Rajendra Kumar Goyal, 2018. Nanomaterials and Nanocomposites: Synthesis, Properties,
Characterization Techniques, and Applications. Taylor & Francis, CRC Press.
[7] S. Noor Mohammad, 2020. Synthesis of Nanomaterials: Mechanisms, Kinetics and Materials
Properties. Springer.
[8] Bhat, A.H., Khan, I., Jawaid, M., Suliman, F.O., Al-Lawati, H., Al-Kindy, S.M., 2019.
Assoc. Prof. Dr. Nguyen Van Dung Nanomaterials for Healthcare, Energy and Environment. Springer.
[9] C. Bréchignac, P. Houdy, M. Lahmani, 2007. Nanomaterials and Nanochemistry. Springer.
Faculty of Chemical Engineering, Ho Chi Minh City University of Technology, VNU-HCM [10] William D. Callister, Jr., David G. Rethwish, 2018. Materials Science and Engineering: An
Introduction (11th ed.). Wiley
Email: [email protected]

3 4
SCALE NANOMETER & NANOSCALE

The prefix ‘nano’ refers to a Greek prefix meaning ‘dwarf’ or


something very small and depicts one thousand millionth of a
meter (10-9 m).

A nanometer is a billionth of a meter. Nanoscale can refer to


things less than 100 nanometers in size or to materials so
small that they behave differently from normal.

Our fingernails grow about a nanometer


every second. That means they grow 86,400
nm in a day, but that’s still too small for us to
notice a difference.
5 6
NANOMETER & NANOSCALE NANOWORLD

The head of a pin 1,000,000 nm The term nanoworld is a mixture of two different terms, i.e., nano and world.
We can see them with The nanoworld consists of four different fields, namely nanomaterials,
The page of a book 100,000 nm thick
our eyes unaided.
nanometrology, electronic nanotechnology, and nanobiotechnology.
A human hair ~40,000 nm thick
A red blood cell ~7,000 nm We can see them using a Nanometrology: the scientific study of measurement at the nanoscale

Bacteria 1,000–5,000 nm light microscope. Electronic nanotechnology refers to the use of nanotechnology in electronic

Transistor on latest computer components. The term covers a diverse set of devices and materials, with the
chips (there are up to 100 100 nm common characteristic that they are so small that inter-atomic interactions and
million of them) We need an electron quantum mechanical properties need to be studied extensively.
microscope or other Nanobiotechnology is the application of nanotechnology in biological fields.
DNA molecule 2 nm wide
devices to see them.
Most atoms 0.1–0.2 nm Nanotechnology is a multidisciplinary field that currently recruits
10 hydrogen atoms side by side 1 nm long approaches, technologies, and facilities available in conventional as well
as advanced ways in engineering, physics, chemistry, and biology.

7 8
NANOSCIENCE NANOTECHNOLOGY

Nanoscience is the study of Nanotechnology is the design, production, and application of


structures and materials on an structures, devices, and systems at the nanoscale. The purpose of
ultra-small scale, and the unique and nanotechnology is to fabricate different types of structures with
interesting properties these unique properties due to their small size. This field includes
materials demonstrate. biosciences, chemistry, physics, and mechanical engineering.
So essentially, nanoscience is studying nanomaterials and their
Nanoscience is cross-disciplinary,
properties and nanotechnology is using those materials and
meaning scientists from a range of
properties to create something new or different.
fields including chemistry, physics,
→ Nanoscience and nanotechnology have the potential to reshape
biology, medicine, computing,
the world around us. They could lead to revolutionary breakthroughs
materials science and engineering
in fields ranging from manufacturing to health care.
are studying it and using it to better
understand our world.
9 10
NANOSCIENCE AND NANOTECHNOLOGY NANOCHEMISTRY

Nanochemistry is an emerging sub-discipline of the chemical and


material sciences that deals with the development of new methods for
creating nanoscale materials. The term "nanochemistry" was first used by
Ozin in 1992 as the uses of chemical synthesis to reproducibly afford
nanomaterials from the atom "up", contrary to the nanoengineering and
Nanoscience is a convergence of physics,
nanophysics approach that operates from the bulk "down“’.
chemistry, and biotechnology, which deal
with the manipulation of materials at Nanochemistry is concerned with the synthesis and characterization of
atomic and molecular scales. nanomaterials and nanoscale structures.
Nanotechnology is the ability to observe,
measure, manipulate, assemble, and
manufacture matter at the nanoscale.

11 12
HISTORY OF NANOTECHNOLOGY HISTORY OF NANOTECHNOLOGY

➢ In 1959, American physicist and Nobel Prize laureate In 1991, Drexler, Peterson and
Richard Phillips Feynman introduced the concept of
Pergamit published another book
nanotechnology. “Why can’t we write the entire 24 volumes
entitled “Unbounding the Future:
of the Encyclopedia Britannica on the head of a pin?”
the Nanotechnology Revolution” in
➢ In 1986, K. Eric Drexler published the first book on Richard Phillips which they use the terms “nanobots”
Feynman (1918 –1988)
nanotechnology “Engines of Creation: The Coming Era or “assemblers” for nano processes
of Nanotechnology”, which led to the theory of “molecular
in medicine applications and then the
engineering” becoming more popular. Drexler described
famous term “nanomedicine” was
the build-up of complex machines from individual atoms,
used for the first time after that.
which can independently control molecules and atoms and
thereby produce self-assembly nanostructures.
Top-down and bottom-up methods
Kim Eric Drexler
(1955)
13 14
HISTORY OF NANOTECHNOLOGY HISTORY OF NANOTECHNOLOGY

The Lycurgus cup: Nanoparticles and structures have been used by humans in The Lycurgus cup
fourth century AD, by the Roman, which demonstrated one of the most interesting In 1990, transmission electron microscopy (TEM) was used to
examples of nanotechnology in the ancient world. explain the dichroism phenomenon in the presence of 50–100
nm of Au-particle size.
The Lycurgus cup, from the British
Museum collection, represents one of the XRD analysis revealed an alloy of 7Ag-3Au and about 10% Cu
most outstanding achievements in the in the glass matrix. Au nanoparticles

ancient glass industry. It is the oldest and The Au nanoparticles produce a red color as a result of light
most famous example of dichroic glass. absorption (~520 cm-1). The red-purple color is due to the
Dichroic (two different colors) glass absorption by bigger particles.
describes two different types of glass that While the green color is attributed to the light scattering by
change color in certain lighting conditions. The Lycurgus cup. The glass appears
colloidal dispersions of Ag nanoparticles with a size >40 nm.
green in reflected light (A) and red-
The glass appears green when light pass The Lycurgus cup is recognized as one of the oldest synthetic
purple in transmitted light (B)
through it from in front. It is red when it is nanomaterials. Ag nanoparticles
lit from behind.

15 16
GENERATIONS OF NANOSTRUCTURES NANOMETER SCALE
17 18
SURFACE AREA-TO-VOLUME RATIO SURFACE AREA-TO-VOLUME RATIO

Nanomaterials are certainly small, but they actually have a comparatively


At the same mass, nanoscale materials have a very large surface area
large surface area. The surface area-to-volume ratio would indicate their rate of
compared to bulk materials.
interaction with the environment per unit volume per unit time.

19 20
LENGTH SCALE & CALCULATION LENGTH SCALE & CALCULATION

The increase in surface area due to the reduction in cube size can be determined from the ratio
of the accumulative surface area of all cubes after the size reduction to the surface area
(A) of a cube before size reduction.
where A and a are the surface areas of a cube before and after size reduction, respectively.

v and l are the volume and edge length of each small-sized


cube.
Nc is the number of smaller cubes.
V and L is the volume and edge length of large-sized cube.

Thus, the reduction of the size of the cube from 1 to 0.1 µm and 0.01 µm will result
in 103 and 106 cubes, respectively.
21 22
LENGTH SCALE & CALCULATION LENGTH SCALE & CALCULATION

EXAMPLE 1 Size effect on surface atoms of spherical particles


How many cubes with each side of 1 nm can be carved out of a cube with each
side of 1 m? Find the collective surface area of the nanometer-sized cubes. Thus, the radii of the particle (RC) =
N1/3.ra and the total number of atoms in
the particles in terms of radii are:

For a spherical-shaped particle, the volume


of the particle = total volume of the atoms The surface area of the particle (Sc)
having atomic radii of ra, that is, can be calculated by using:

23 24
LENGTH SCALE & CALCULATION NANOPARTICLES

NPs are particles with a diameter size less than 100 nm.
Therefore they are zero dimensional (0D) nanomaterials.

The fraction of atoms at the surface


is called dispersion (F). In other
words, the ratio of the surface atoms
to the total number of atoms (i.e., F)
can be calculated by using:
25 26
NANOPARTICLES NANOMATERIALS

1/ Natural nanoparticles Nanomaterials are materials that are studied and synthesized at the nanoscale.
Organic: Fungi, coal, bacteria, and many others. Nanoscale materials are those whose at least one dimension is less than the
Inorganic: Carbonates, silicates, metal sulfides and oxides, and so on. nanoscale (<100 nm).

2/ Anthropogenic nanoparticles (development of human beings)


Organic: Soot, fly ash, and carbon nanotube
Inorganic: SiO2, TiO2, and ZnO
a/ Incidental NPs are formed unintentionally, do not have well-defined
shapes and sizes. Examples: cooking smoke, diesel exhaust, welding fumes,
industrial effluents, sandblasting
b/ Engineered NPs are intentionally created NPs for different purposes.
Examples: Quantum dots (0D)
NPs, nanoshells, and microcapsules (3D)
Nanotubes, fibers, and nanowires (2D)
Nanosheets, thin films, layers, and coatings (1D)

27 28
CLASSIFICATION OF NANOMATERIALS CLASSIFICATION OF NANOMATERIALS
29 30
APPLICATIONS NANOTECHNOLOGY IN AUTOMOBILE INDUSTRIES

31 32
NANOTECHNOLOGY IN MEDICINE QUANTUM EFFECTS
33 34
Wave-particle duality Electromagnetic waves & Energy quanta

The concept of wave-particle duality is the interface between


classical and quantum mechanics, according to which, light has two
natures simultaneously, that is, a wave nature and a particle nature.

Classically, it was considered that waves and particles are different In the classical domain, it is thought
things, but in quantum mechanics, they are interconnected. Particles
that electric and magnetic waves
carry energy and momentum in localized small mass and waves are consist of electric and magnetic
the motion of disturbance that transfers energy.
fields with specific wavelengths.
More info: Wave–particle duality

35 36
The de Broglie hypothesis Evidence for the wave nature of electrons

It is evident that if v = 0, then λ = , and if v = , then λ = 0, which


shows that waves are associated with each material particle if they
are in motion. Since microscopic particles have a dual nature and due
to their wave nature, the exact location of these particles cannot be
measured, which implies an uncertainty in the position of these
particles.

More info: Link


37 38
Evidence for the wave nature of electrons Evidence for the wave nature of electrons

39 40
Evidence for the wave nature of electrons Heisenberg’s uncertainty principle

Δx is the uncertainty in the measurement of position.


ΔP is the uncertainty in the measurement of momentum.

➢ It is impossible to simultaneously determine the momentum and


position of a particle with perfect accuracy. So, there is always a
fundamental uncertainty in the measurement of these physical
quantities.

More info: Link


41 42
Quantum dots Moore’s law

A semiconductor crystal with tunable optical and electronic properties by Moore’s law is an observational law in which it was predicted that the
controlling its three dimensional size less than 100 nm is called quantum number density of transistors would double on integrated circuits (ICs) every
dot (QD). In general, QDs are atomic clusters or nanocrystallites that year. It was predicted by Gordon Moore, cofounder of Intel, in 1965, that
consist of about 102 – 106 atoms having less than 100 free electrons. this growth rate would remain so for at least 10 years.
QDs are classified into three types based on their electron confinement, The new definition of Moore’s law is, the number of micro-components that
that is, planar, vertical, or self-assembled QDs. could be placed in an integrated circuit or microchip and lowest
Researchers are taking great interest in the optical and electronic manufacturing cost was doubling every 18 months which accounts for the
properties of quantum dots due to their importance in novel applications improvement in the speed of the computers.
over the past two decades. On the other hand, QDs are toxic, which This trend would likely continue accurately into the future for a few decades.
prohibits their use in medical applications in future. QDs can damage Moore’s second law: It states that the cost of a transistor chip or IC
DNA and disturb the normal activity of cells. manufacturing factory doubles every four years.

More info: Quantum dot More info: Moore's law

43 44
Moore’s law Moore’s law
45 46
Quantum tunneling Quantum tunneling

Tunneling is a quantum mechanical phenomenon by which small


particles like electrons can pass through a barrier of some potential
without sufficient energy, which they classically would not be able to
do because they do not have sufficient energy.

Tunneling plays an essential role in modern physical, chemical, and


biological phenomena like the effect of large kinetic isotopes in
chemicals reactions, radioactive decay, superconductor devices, and
semiconductor devices.

More info: Quantum tunnelling


Tunnel diode
Dr. Nguyen Van Dung, Faculty of Chemical Engineering, HCMUT

47 48
Quantum tunneling Quantum tunneling
49 50
Quantum tunneling INTERFACES AND SURFACES

➢ An interface is the thin border between two localized phases of matter.


This thin boundary is called an interface for any physical state of mater.

➢ Specifically, when this interface exists between any condensed state and
a gas or vacuum then it is called a surface. Interface is a more general
term that can be used rather than surface.

51 52
INTERFACES AND SURFACES INTERFACES AND SURFACES
53 54
Surface physics and chemistry Surface modification

55 56
Surface scratching/roughening Surface scratching/roughening (cào/làm nhám)

Surface can be altered using plasma deposition, chemical-based etching.

More info: Link


57 58
Surface patterning Chemical surface modification

✓ Plasma vapor deposition (PVD): Lắng động pha hơi plasma

✓ Chemical vapor deposition (CVD): Lắng đọng pha hơi hóa học

✓ Grafting: Ghép (bằng quang năng hay hóa học)

✓ Self-assembled monolayers (SAMs): Tự ghép

More info:
doi.org/10.3390/polym13030445 PDF
doi.org/10.3390/nano11082079 PDF

59 60
Chemical surface modification Chemical surface modification

More info: 10.3390/polym10050527


(PDF)

More infor: DOI:10.3389/fmats.2020.00039 (PDF)


61 62
Self-assembled monolayers Self-assembly

➢ Self-assembled monolayers (SAM) of organic molecules are


molecular assemblies formed spontaneously on surfaces by
adsorption and are organized into more or less large ordered
domains. More info: Link

More info: Link PDF

63 64
Self-assembly Thin-film deposition

The process of adding an exceptionally thin layer ranging from


5 nm to 100 μm in thickness on a substrate surface is known
as thin-film deposition.
More info: Link
PDF1 PDF2
65 66
Thin-film deposition Physical vapor deposition

✓ Solar panels with thin films


for energy production

✓ Aluminized PET films for


food packaging

✓ Cutting tools coated with


titanium nitride

✓ More info: PVD

Coatings on glass: PDF

67 68
Chemical vapor deposition Electroplating

More info: CVD CNT PDF

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