Chapter 1-1-Introduction To Nanochemistry

NANOCHEMISTRY & APPLICATIONS
CHAPTER 1-1:
INTRODUCTION TO NANOCHEMISTRY
Dr. Nguyen Van Dung

Faculty of Chemical Engineering, Ho Chi Minh City University of Technology (HCMUT)
Email: nvdung@hcmut.edu.vn
Dr. Nguyen Van Dung, Faculty of Chemical Engineering, HCMUT

2
REFERENCES
[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.
[3] Anatoliy Petrovych Shpak, Petr Petrovych Gorbyk, 2010. Nanomaterials and Supramolecular:
Structures Physics, Chemistry, and Applications. Springer.
[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.
Nanomaterials for Healthcare, Energy and Environment. Springer.
[9] C. Bréchignac, P. Houdy, M. Lahmani, 2007. Nanomaterials and Nanochemistry. Springer.
[10] William D. Callister, Jr., David G. Rethwish, 2018. Materials Science and Engineering: An
Introduction (11th ed.). Wiley

3
SCALE

4
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
NANOMETER & NANOSCALE
The head of a pin 1,000,000 nm

We can see them with
The page of a book 100,000 nm thick
our eyes unaided.
A human hair ~40,000 nm thick
A red blood cell ~7,000 nm We can see them using a
Bacteria 1,000–5,000 nm light microscope.
Transistor on latest computer

chips (there are up to 100 100 nm
million of them) We need an electron
microscope or other
DNA molecule 2 nm wide
devices to see them.
Most atoms 0.1–0.2 nm
10 hydrogen atoms side by side 1 nm long

6
NANOWORLD
The term nanoworld is a mixture of two different terms, i.e., nano and world.
The nanoworld consists of four different fields, namely nanomaterials,

nanometrology, electronic nanotechnology, and nanobiotechnology.
Nanometrology: the scientific study of measurement at the nanoscale
Electronic nanotechnology refers to the use of nanotechnology in electronic

components. The term covers a diverse set of devices and materials, with the
common characteristic that they are so small that inter-atomic interactions and
quantum mechanical properties need to be studied extensively.
Nanobiotechnology is the application of nanotechnology in biological fields.
Nanotechnology is a multidisciplinary field that currently recruits approaches,

technologies, and facilities available in conventional as well as advanced ways
in engineering, physics, chemistry, and biology.
Dr. Nguyen
Dr. Nguyen Van Dung, Faculty
Van Dung, Faculty of
of Chemical
Chemical Engineering,
Engineering, HCMUT
HCMUT
7
NANOSCIENCE
Nanoscience is the study of

structures and materials on an
ultra-small scale, and the unique and
interesting properties these
materials demonstrate.
Nanoscience is cross-disciplinary,
meaning scientists from a range of
fields including chemistry, physics,
biology, medicine, computing,
materials science and engineering
are studying it and using it to better
understand our world.

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NANOTECHNOLOGY
Nanotechnology is the design, production, and application of

structures, devices, and systems at the nanoscale. The purpose of
nanotechnology is to fabricate different types of structures with
unique properties due to their small size. This field includes
biosciences, chemistry, physics, and mechanical engineering.
So essentially, nanoscience is studying nanomaterials and their
properties and nanotechnology is using those materials and
properties to create something new or different.
→ Nanoscience and nanotechnology have the potential to reshape
the world around us. They could lead to revolutionary breakthroughs
in fields ranging from manufacturing to health care.
Dr. Nguyen
of Chemical
Engineering, HCMUT
HCMUT
9
NANOSCIENCE AND NANOTECHNOLOGY
Nanoscience is a convergence of physics,

chemistry, and biotechnology, which deal
with the manipulation of materials at
atomic and molecular scales.
Nanotechnology is the ability to observe,
measure, manipulate, assemble, and
manufacture matter at the nanoscale.

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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
nanophysics approach that operates from the bulk "down“’.
Nanochemistry is concerned with the synthesis and characterization of

nanomaterials and nanoscale structures.

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HISTORY OF NANOTECHNOLOGY
• In 1959, American physicist and Nobel Prize laureate

Richard Phillips Feynman introduced the concept of
nanotechnology. “Why can’t we write the entire 24 volumes
of the Encyclopedia Britannica on the head of a pin?”
• In 1986, K. Eric Drexler published the first book on Richard Phillips

Feynman (1918 –1988)
nanotechnology “Engines of Creation: The Coming Era of
Nanotechnology”, which led to the theory of “molecular
engineering” becoming more popular. Drexler described
the build-up of complex machines from individual atoms,
which can independently control molecules and atoms and
thereby produce self-assembly nanostructures.
Kim Eric Drexler
(1955)

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In 1991, Drexler, Peterson and

Pergamit published another book
entitled “Unbounding the Future:
the Nanotechnology Revolution” in
which they use the terms “nanobots”
or “assemblers” for nano processes
in medicine applications and then the
famous term “nanomedicine” was
used for the first time after that.
Top-down and bottom-up methods

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The Lycurgus cup

Nanoparticles and structures have been used by humans in fourth century AD, by the Roman,
which demonstrated one of the most interesting examples of nanotechnology in the ancient
world.
The Lycurgus cup, from the British Museum
collection, represents one of the most
outstanding achievements in the ancient
glass industry. It is the oldest and most
famous example of dichroic glass. Dichroic
(two different colors) glass describes two
different types of glass that change color in
certain lighting conditions. The Lycurgus cup. The glass appears green in
reflected light (A) and red-purple in
The glass appears green when light pass transmitted light (B)
through it from in front. It is red when it is
lit from behind.
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The Lycurgus cup

In 1990, transmission electron microscopy (TEM) was used to
explain the dichroism phenomenon in the presence of 50–100
nm of Au-particle size.
XRD analysis revealed an alloy of 7Ag-3Au and about 10%
Cu in the glass matrix. Au nanoparticles
The Au nanoparticles produce a red color as a result of light

absorption (~520 cm-1). The red-purple color is due to the
absorption by bigger particles.
While the green color is attributed to the light scattering by
colloidal dispersions of Ag nanoparticles with a size >40 nm.
The Lycurgus cup is recognized as one of the oldest synthetic
Ag nanoparticles
nanomaterials.
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GENERATIONS OF NANOSTRUCTURES

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NANOMETER SCALE

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SURFACE AREA-TO-VOLUME RATIO
Nanomaterials are certainly small, but they actually have a comparatively

large surface area. The surface area-to-volume ratio would indicate their rate of
interaction with the environment per unit volume per unit time.
Dr. Nguyen
of Chemical
Engineering, HCMUT
HCMUT
18
SURFACE AREA-TO-VOLUME RATIO
At the same mass, nanoscale materials have a very large surface area
compared to bulk materials.
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LENGTH SCALE & CALCULATION
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.

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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.
Dr. Nguyen
of Chemical
Engineering, HCMUT
HCMUT
21
EXAMPLE 1
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.

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Size effect on surface atoms of spherical particles

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:

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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:

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

25
NANOPARTICLES
1/ Natural nanoparticles
Organic: Fungi, coal, bacteria, and many others.
Inorganic: Carbonates, silicates, metal sulfides and oxides, and so on.
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)
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NANOMATERIALS
Nanomaterials are materials that are studied and synthesized at the nanoscale.
Nanoscale materials are those whose at least one dimension is less than the
nanoscale (<100 nm).

27
CLASSIFICATION OF NANOMATERIALS

28
CLASSIFICATION OF NANOMATERIALS
Dr. Nguyen
of Chemical
Engineering, HCMUT
HCMUT
29
APPLICATIONS

30
NANOTECHNOLOGY IN AUTOMOBILE INDUSTRIES

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NANOTECHNOLOGY IN MEDICINE

32
QUANTUM EFFECTS

33
Wave-particle duality
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

things, but in quantum mechanics, they are interconnected. Particles
carry energy and momentum in localized small mass and waves are
the motion of disturbance that transfers energy.
More info: Wave–particle duality
Dr. Nguyen
of Chemical
Engineering, HCMUT
HCMUT
34
Electromagnetic waves & Energy quanta
In the classical domain, it is thought

that electric and magnetic waves
consist of electric and magnetic
fields with specific wavelengths.

35
The de Broglie hypothesis
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

36
Evidence for the wave nature of electrons

37

38

39
Dr. Nguyen
of Chemical
Engineering, HCMUT
HCMUT
40
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
Quantum dots
A semiconductor crystal with tunable optical and electronic properties by

controlling its three dimensional size less than 100 nm is called quantum
dot (QD). In general, QDs are atomic clusters or nanocrystallites that
consist of about 102 – 106 atoms having less than 100 free electrons.
QDs are classified into three types based on their electron confinement,
that is, planar, vertical, or self-assembled QDs.
Researchers are taking great interest in the optical and electronic

properties of quantum dots due to their importance in novel applications
over the past two decades. On the other hand, QDs are toxic, which
prohibits their use in medical applications in future. QDs can damage
DNA and disturb the normal activity of cells.
More info: Quantum dot

42
Moore’s law
Moore’s law is an observational law in which it was predicted that the

number density of transistors would double on integrated circuits (ICs) every
year. It was predicted by Gordon Moore, cofounder of Intel, in 1965, that
this growth rate would remain so for at least 10 years.
The new definition of Moore’s law is, the number of micro-components that
could be placed in an integrated circuit or microchip and lowest
manufacturing cost was doubling every 18 months which accounts for the
improvement in the speed of the computers.
This trend would likely continue accurately into the future for a few decades.
Moore’s second law: It states that the cost of a transistor chip or IC
manufacturing factory doubles every four years.
More info: Moore's law

43
Moore’s law

44
Moore’s law

45
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
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Quantum tunneling

47
Quantum tunneling

48
Quantum tunneling

49
Quantum tunneling
Dr. Nguyen
of Chemical
Engineering, HCMUT
HCMUT
50
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
Dr. Nguyen
of Chemical
Engineering, HCMUT
HCMUT
52

53
Surface physics and chemistry
Dr. Nguyen
of Chemical
Engineering, HCMUT
HCMUT
54
Surface modification

55
Surface scratching/roughening
Surface can be altered using plasma deposition, chemical-based etching.

56
Surface scratching/roughening (cào/làm nhám)
More info: Link

57
Surface patterning
More info:
doi.org/10.3390/polym13030445 PDF
doi.org/10.3390/nano11082079 PDF
Dr. Nguyen
of Chemical
Engineering, HCMUT
HCMUT
58
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

59
More infor: DOI:10.3389/fmats.2020.00039 (PDF)

Dr. Nguyen
of Chemical
Engineering, HCMUT
HCMUT
60
More info: 10.3390/polym10050527

(PDF)

61
Self-assembled monolayers
➢ 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

62
Self-assembly
More info: Link PDF

63
Self-assembly
More info: Link

PDF1 PDF2

64
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.
Dr. Nguyen
of Chemical
Engineering, HCMUT
HCMUT
65
Thin-film deposition

66
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
Dr. Nguyen
of Chemical
Engineering, HCMUT
HCMUT
67
Chemical vapor deposition
More info: CVD CNT PDF

68
Electroplating
Dr. Nguyen
of Chemical
Engineering, HCMUT
HCMUT

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NANOCHEMISTRY & APPLICATIONS

Dr. Nguyen Van Dung

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

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

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

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

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

Our fingernails grow about a nanometer

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

The head of a pin 1,000,000 nm

Transistor on latest computer

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

The nanoworld consists of four different fields, namely nanomaterials,

Nanometrology: the scientific study of measurement at the nanoscale

Electronic nanotechnology refers to the use of nanotechnology in electronic

Nanobiotechnology is the application of nanotechnology in biological fields.

Nanotechnology is a multidisciplinary field that currently recruits approaches,

Nanoscience is the study of

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

Nanotechnology is the design, production, and application of

Nanoscience is a convergence of physics,

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

Nanochemistry is an emerging sub-discipline of the chemical and

Nanochemistry is concerned with the synthesis and characterization of

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

• In 1959, American physicist and Nobel Prize laureate

• In 1986, K. Eric Drexler published the first book on Richard Phillips

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

In 1991, Drexler, Peterson and

Top-down and bottom-up methods

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

The Lycurgus cup

The Lycurgus cup

The Au nanoparticles produce a red color as a result of light

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

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

Nanomaterials are certainly small, but they actually have a comparatively

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

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

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

Size effect on surface atoms of spherical particles

For a spherical-shaped particle, the volume

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

The fraction of atoms at the surface

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

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

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

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

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

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

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

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

The concept of wave-particle duality is the interface between

Classically, it was considered that waves and particles are different

More info: Wave–particle duality

In the classical domain, it is thought

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

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

More info: Link

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

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

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

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