CHAPTER 1

Nanotechnology and Chemistry:

The Unseen Scale with
Magnificent Impact

1.1 Introduction

‘‘There’s Plenty of Room at the Bottom.’’

This was the title of physicist Richard Feynman’s talk on December 29,
1959, at the Annual Meeting of the American Physical Society at The
California Institute of Technology (Caltech). In that talk, Feynman asked
many questions widely believed to be illogical at the time. Feynman be-
lieved that if we were able to control matter at the atomic or molecular
scale, we could achieve many practical advances that could revolutionize
technology and production processes.1
Feynman posed many questions related to very small-scale systems and
their enormous usefulness. For example, he discussed how the small size of
living cells aids in executing important functions for living organisms.
Feynman proposed an idea that if we could have the ability to manipulate
things as small as atoms and molecules, that these manipulations could be
used in a limitless range of technological applications. He imagined that if
we could control small-scale substances, we could create materials with new
chemical and physical properties for new applications. Essentially, Feynman
focused his talk on the idea of nanoscience and nanotechnology, but he
never explicitly stated it.1

Advances in Chemistry Education Series No. 9

Nanochemistry for Chemistry Educators
By Riam Abu Much, Kurt Winkelmann and Muhamad Hugerat
r Riam Abu Much, Kurt Winkelmann and Muhamad Hugerat 2022
Published by the Royal Society of Chemistry, www.rsc.org

1
2 Chapter 1

1.1.1 What Is Nano and Why Is It Important?

Linguistically, the word ‘‘nano’’ is derived from the Greek word pertaining to
dwarf, which refers to very small things. One nanometre (nm) is equal to one
billionth of a meter (0.000 000 001 m). Here are some relative comparisons
which describe the nanometre scale:

 If a one mm section on a ruler is divided into one million equal parts,

this is one nanometre in length.
 The average diameter of human hair is about 60 000 to 100 000
nanometres.
 A sheet of paper is about 100 000 nanometres thick.
 Ten hydrogen atoms lined up is equal to one nanometre.

Nanoscience and nanotechnology are multidisciplinary scientific fields

that deal with the preparation, processing and application of materials,
devices, and systems at the nanometre scale. These fields have attracted
great interest among scientists and researchers, which has led to many
developments that are used in our daily life.2
Nanomaterials are materials that have at least one dimension in the nano-
metre scale. Scientists discovered that nanoscale-sized materials demonstrate
different physical and chemical properties compared to their larger counter-
parts. For example, gold (Au) displays known, familiar properties of being: (i) a
gold-colored, soft, and shiny metal; (ii) a good conductor of heat and electricity;
(iii) chemically inert (making it widely used in the jewellery industry); and (iv)
its melting point could reach 1064 1C.63 These properties are present in gold, in
dimensions larger than the nanometre range. Reducing the size of gold to the
nanometre scale causes drastic changes in its characteristic properties. For
example, nanometre-sized gold is not characterized as gold in color. In the
nanometre size range, it also becomes a semiconductor, good catalyst, and its
melting point reduces to 300 1C (Table 1.1). Many materials at the nanoscale
exhibit unique optical, electrical, magnetic, and chemical properties which
their larger counterparts do not possess. These unique nanoscale properties
have a great impact in technology and medicine. Nanomaterials have become
basic components of everyday, modern technologies, and major players in
twenty-first century technological advances.3,4

1.2 Why Do Properties of Materials Change at the

Nanoscale?
Two main effects are responsible for the differences of material properties
when sized in nanoscale.

1.2.1 Surface Area–Volume Ratio

Physical properties and kinetics of reactions are strongly related to the
number of particles that are exposed to the surrounding environment. This
Nanotechnology and Chemistry 3
Table 1.1 Physical and chemical properties of gold at the macro-
scale and nanoscale.

Small pieces of gold at the

Gold (regular size) nanometre scale
Always gold in color Never gold in color
Soft metal Not a metal but semiconductor
Chemically inert Could kill cancer cells
Melting point 1064 1C Melting point 300 1C

means that the material surface area is the central feature which affects re-
activity. Subdividing materials into smaller parts maintains an item’s volu-
metric size but its collective surface area increases. For example, a cube with
dimensions of 1 cm1 cm1 cm has a volume of 1 cm3, and the area of its six
surfaces equals 6 cm2. By dividing the cube into one million smaller cubes of
0.1 mm0.1 mm0.1 mm, the whole cube maintains its total volume, but
simple calculations reveal that after this division, the collective total surface
area of the cubes becomes 100-fold larger than that of the original cube. If the
cube is divided further into smaller, non-visible cubes with dimensions of
1 nm1 nm1 nm, its surface area increases by 10 million (see Sections
6.2.1, 6.2.4, Chapter 6, and 5.2.1.1, 5.2.2.2, 5.3.2, Chapter 5).
Nanoscale-sized materials possess greater surface areas than the same
amount of their larger-sized counterparts of the same material (Figure 1.1).
This is because the number of atoms and molecules that were previously
inside the materials are exposed and become surfaces. This presents a
particularly unique and interesting phenomenon at the nanoscale: nano-
materials with extremely high surface area to volume ratios will interact with
the surrounding environment more intensively. The large surface areas of
nanomaterials influence innate properties, such as the melting point,
density, solubility, mechanical properties, electrical conductivity, surface
tension, catalytic activity, and spectroscopic properties.5–11

1.2.2 Quantum Confinement Effect

The quantum confinement effect is observed when a material size affects its
electronic and optical properties. That is, when a semiconductor material
absorbs a photon with an energy equal to or higher than its bandgap, it
promotes an electron from the valence to the conduction band. This event
leaves a hole in the valence band and an exciton is then formed. An exciton is
an electron–hole pair associated with coulomb electrostatic interactions
between the hole and the promoted electron. According to the rules of
quantum mechanics, the distance between the hole and the promoted
electron is the Bohr exciton radius. A typical semiconductor material is
4 Chapter 1

Figure 1.1 Total surface area increases while cutting cube to smaller cubes.

Figure 1.2 Schematic illustration of quantum confinement effect.

larger than the radius of the Bohr exciton when the electron motion is not
confined or restricted. On the other hand, when reducing the size of a ma-
terial to the nanoscale, the material size will lessen to be smaller than the
radius of the bulk Bohr exciton. This leads to confinement of electron mo-
tion and a congested arrangement of electron holes, resulting in quantum
confinement of the electron hole pairs. Consequently, the bandgap in-
creases, and discrete energy levels appear. This increased bandgap creates
differing optical and electrical properties. As a result, nanoscale-sized ma-
terials could appear to be different colors not normally associated with
larger-sized materials of the same type (Figure 1.2).5,12–17
Nanotechnology and Chemistry 5

1.3 Types of Nanostructured Materials

The most common method to classify nanosized materials is based on the
number of dimensions that are not at the nanoscale range. Accordingly, four
categories of nanomaterials are classified as the following:

(i) Zero-dimensional (0D) nanomaterials range from 1 to 100 nm in each

spatial dimension. That is, electron confinement that occurs in all
x, y, and z directions.
(ii) One-dimensional (1D) structures are nanoscale in two dimensions,
and one dimension is on the macroscale. Electron confinement
occurs in two dimensions, and in one dimension the electrons are
free to move along it.
(iii) Two-dimensional (2D) structures consist of one dimension confined
to the nanoscale and two dimensions in the macroscale. Electron
confinement exists in one dimension, while in the other two mac-
roscale dimensions the electrons are free to move.
(iv) Three-dimensional (3D) structures do not have dimensions in
nanoscale. Therefore, they do not have electron confinement in the
nano range and electrons move freely along all three x, y, and z
directions. Figure 1.3 illustrates the four types of nanostructured
materials according to their number of nanoscale dimensions.18

Each category of nanomaterials consists of differing types of nanostructures

which are categorized according to their shape, morphology, characteristics,
and application. The most common representation of 0D nanomaterials are
nanoparticles and quantum dots (QD). Nanoparticles are defined as small
nanostructured materials with sizes ranging from 1 to 100 nm. The properties
of nanoparticles are directly related to their size. Nanomaterial properties
change when their size approaches the nanoscale as this increases the ratio of
atoms on their surfaces.
Metal nanoparticles, such as gold and silver particles, are distinguished
from other nanomaterials by their unique optical properties that arise from a
phenomenon called localized surface plasmon resonance (LSPR). LSPR refers

Figure 1.3 Types of nanostructured materials based on number of nanoscale

dimensions.
6 Chapter 1

Figure 1.4 Schematic illustration of localized surface plasmon resonance (LSPR) of

metal Nanoparticles.

to when metal nanoparticles are irradiated with electromagnetic radiation

and the wavelength of the light becomes much longer than the size of the
nanoparticles, inducing oscillation of conduction electrons when interacting
with the light. This oscillation around the surface of the nanoparticles causes
a dipole to oscillate along the direction of the electric field of light.
The amplitude of the oscillation reaches its maximum at a specific frequency,
thereby denoted as LSPR. The LSPR induces strong absorption of incident
light, which can be measured with ultraviolet–visible absorption spectroscopy
(UV–vis). This phenomenon is responsible for the unique, unfamiliar colors of
the different metallic nanoparticles, illustrated in Figure 1.4.
The LSPR phenomenon is affected by the size and shape of metal nano-
particles. For example, gold nanoparticles have fascinated scientists because
of their ability to display a variety of colors, due to the collective oscillation of
the electrons at the surface of the nanoparticles, as previously described
earlier in this section. Optical absorption is also strongly dependent on the
size of gold nanoparticles. Consequently, gold nanoparticles can appear red,
orange, purple, and even blue. To produce glossy sheens, nineteenth century
artists exploited the colorful range of metallic nanoparticles by applying
them onto vessel surfaces or producing stained glass.
Quantum dots are nanostructured particles made of semiconductor ma-
terials. In comparison to nanoparticles, the size of quantum dots ranges
from 1 to 10 nm, less than the size of nanoparticles. Quantum dots are
strongly characterized by the electron confinement effect and this is re-
flected by their unique array of colors.19
One of the molecular allotropes of carbon is fullerene C60. Fullerene exists
as a 0D nanoparticle consisting of sp2 hybrid carbon atoms arranged in five-
and six-membered rings, and is widely used in electronics, biology, and
medicine.
Nanowires and nanotubes are 1D nanostructures and are characterized by
diameters between 1 and 100 nm. Their lengths are much larger than their
diameter range. A nanowire is defined as any solid material in the form of a
wire with the diameter in the nanoscale range. The ratio between the length
of nanowire and its nanoscale diameter is called the aspect ratio. Typical
nanowires have aspect ratios of 1000 or more, which signifies that its length
Nanotechnology and Chemistry 7

is at least 1000 times longer that its diameter. Differing types of nanowires
include metallic, semiconductor, and molecular nanowires. All nanowire
types are composed of repeating molecular units of organic or inorganic
materials. Two nanowire dimensions are affected by quantum confinement
due to their sizes being in nanoscale. The length of nanowire is not on the
nanoscale and therefore the quantum confinement effect does not take place.
Nanotubes are hollow nanowires with a cylindrical shape. The most well-
known nanotubes are called single-walled carbon nanotubes (SWCNT) and
they consist of rolled up graphene sheets. Graphene is one of the allotropic
structures of carbon. Graphene is a single layer of graphite that is made up
of carbon atoms organized into hexagonal shapes. Each graphene carbon
atom bonds to three other carbon atoms and leaves one electron in free
motion, thus causing high electrical conductivity.
Carbon nanotubes are cylindrical structures made up of graphene sheets
with diameters in the nanoscale and lengths in the macroscale. Carbon
nanotubes are known for their strength and rigidity, stemming from the
strong covalent bonds formed between their carbon atoms. Another form of
carbon nanotube is the multiple-walled carbon nanotube (MWCNT), com-
posed of multiple layers of graphene. Each nanotube in a MWCNT is con-
sidered a single molecule consisting of millions of carbon atoms. Carbon
nanotubes have tremendous electrical, thermal, and mechanical properties
that make them attractive candidates in the development of novel materials
and applications, including biomedical applications, biosensors, and energy
storage. A schematic representation of nanowires and nanotubes is shown in
Figure 1.5a and b respectively.20
Thin layer structures or nanosheets are typical examples of 2D nanostruc-
tures, as the thickness of a nanosheet is in nanoscale. The most well-known
nanosheet is graphene. As shown in Figure 1.6, graphene sheets are composed
of carbon atoms where each atom is bonded to three other ones and packed
into a sequence of hexagonal shapes. On the other hand, single-walled carbon
nanotubes and multiple-walled carbon nanotubes are 1D nanostructures
made of cylindrical structures of graphene sheets.21
Three-dimensional nanostructures are not confined to the nanometre
scale in any dimension. This means all three dimensions are at the

Figure 1.5 Schematic description of: 1.5a, nanowire and 1.5b, nanotube.
8 Chapter 1

Figure 1.6 An illustration of graphene sheet structure, single-walled carbon nano-

tube, and multiple-walled carbon nanotube.

Figure 1.7 Nanostructures of Morpho butterfly wings.

macroscale and the electrons are free to move in all three dimensions. Three-
dimensional nanostructures can be composed of dispersed nanoparticles,
nanowires, and nanotubes.22 In nature, many examples of 3D nanostruc-
tures exist, including the blue, iridescent-colored wings of the morpho
butterfly (Morpho achilles). It was discovered that the unique, blue-colored
wings of the morpho butterfly are composed of multilayered 3D nano-
structures, as illustrated in Figure 1.7.64

1.4 History of Nanomaterials

Recent studies have shown that the use of nanostructured materials began in
antiquity, without intent or awareness of the ideas of nanoscience and
Nanotechnology and Chemistry 9

Figure 1.8 An image in which ancient Egyptian blue was used.

nanotechnology.23 Five thousand years ago, Egyptian civilization was known

to produce a unique, bright blue dye called Egyptian blue (Figure 1.8). In that
period, the dye was used frequently throughout the Middle East for painting,
statues, tombs, and more. This dye was characterized by its unparalleled blue
color that resulted from copper being one of its main components. It ranged
in color from light to dark blue, depending upon its composition. Recent
studies have proven that this unique blue dye is composed of a mixture of
Cuprorivaite (CaCuSi4O10), or calcium copper tetrasilicate, and silicon dioxide
(SiO2) nanoparticles. These compounds are heated to high temperatures
ranging between 800–900 1C in order to produce they dye’s characteristic
range of blue colors. After the end of the Roman era, the Egyptian blue dye , its
components and method for creation were lost and ended up in limbo.24–26
The production of colored stain glass was a notable trend in Europe the
years of 1200–1000 BC, the late Bronze Age. A red glass discovered in the
Italian locale of Frattesina di Rovigo is found to be composed of copper
nanoparticles. Similarly, red Celtic enamel from 400–100 BC is also found to
be composed of copper nanoparticles.27
In the fourth or fifth century AD, Romans used gold and silver nano-
particles to create the famous Lycurgus Cup. The cup appears to be one of
two different colors, depending on the direction of light passing through it.
When light passes from the front, the cup appears green. When light passes
through from behind, the cup appears red. Studies attributed this dichroism
(two colors) phenomenon to the unique effects produced by the cup’s gold
and silver nanoparticles.28
The Damascus Sword was produced some time between the eighth and
seventeenth centuries and was characterized by its unique combination of
flexibility and strength. Although swords are known to be made of steel, the
rigidity of the steel depends on its carbon and iron concentrations and ratios.
10 Chapter 1

Figure 1.9 An image of the ancient Damascus sword.

The French and Russians attempted to duplicate the strong and flexible
features of the Damascus Sword in the early eighteenth century. However,
their attempts were proven unsuccessful, and they were unable to discover
the secret behind its production. In 2006, scientists were able to reveal the
production secret behind the sword’s unique features. The Damascus Sword,
which is presented in Figure 1.9, contained carbon nanotubes, one of the
most durable and flexible materials known to this day.29
As discussed above in Section 1.3, metal nanoparticles are characterized
by their distinctive colors that differ from their familiar color when they are
at the macroscale due to the phenomenon of LSPR. In Europe during the
Middle Ages, in order to color medieval stained glass, glass windows in
churches were painted with distinctive metal nanoparticle colors (see
Figure 1.10). It was discovered in later years that these colors consisted of
solutions of nanoparticles of silver, gold and copper.30,31
In 1857, nanoscience and nanotechnologies were first introduced to the
scientific arena by an English scientist named Michael Faraday. He developed
the first scientific procedure to produce the ruby color of gold nanoparticles
dispersed in an aqueous solution. In 1908, the scientist Mie explained that the
appearance of different metal colors at the nanoscale was due to the theory of
quantum size effects.32 In 1940, silicon dioxide SiO2 nanoparticles were first
produced and used as additives for black carbon in rubber reinforcement.33
Later, in 1959, Richard Feynman famously lectured at the meeting of the
American Physical Society under the title of: ‘‘There is Plenty of Room at
the Bottom’’.1 Here he postulated, ‘‘what would scientists be able to do if
they could control the material at the atom and molecular scale and re-
arrange it as they want?’’. He also described a new field of science dealing
with individual atoms and molecules to make materials and machines with
distinctive properties. This was the first known mention of a new field later
termed nanotechnology.1
The year 1974 was the first time the term ‘‘nanotechnology’’ was used to
describe different methods to produce very small particles.34 In 1976, the
Nanotechnology and Chemistry 11

Figure 1.10 An image of medieval colored stained glass.

Palestinian–American particle physicist Munir Nayfeh renewed a laser

technique to detect and measure individual atoms with the highest levels of
accuracy and control. He succeeded in detecting one atom out of millions
and could revealed its identity for the first time in history; his method was
based on excitation of atoms by laser beams.35 Based on Munir Nayfeh’s
discovery, the Swiss researchers Gerd Ping and Henrik Rohr invented the
Scanning Tunnelling Microscope in 1981.36 For the first time in history, this
microscope allowed scientists to directly image and manipulate atoms and
molecules in order to create nanoparticles. In 1991, the Japanese researcher
Sumio Lijima invented carbon nanotubes. With their unique mechanical
and electronic properties, the creation of carbon nanotubes enabled the
manufacturing of distinctive nanostructures.37

1.5 From the Optical to Electron Microscope: Seeing

at the Nanoscale
Many scientific applications in biology, chemistry, and physics require
observing and viewing extremely small sample sizes that are invisible to the
naked eye. In the late sixteenth century, optical microscopy was invented as a
tool for magnifying and observing very small objects. An optical micro-
scope’s technology is based on the use of visible light rays and different lens
types in order to magnify a sample. The magnification process depends on
shining a light directly onto the sample in a two-lens system. From there, the
optical microscope is able to enlarge objects up to a maximum of 2000 times.
12 Chapter 1

This assists the user in being able to view microorganisms and cells in the
micrometre size range. However, the limited magnification power of the
light microscope was not ideal for scientists and researchers whose research
required viewing and analyzing objects in size ranges smaller than the
microscale.38
In 1931 the electron microscope was invented by German engineers Ernst
Ruska and Max Knoll. The principal adaptation to microscopic technology
used in the electron microscope was to use rays of electrons instead of visible
light. Wave properties of electrons were discovered in a cathode ray experi-
ment performed by J. J. Thomson in 1897. Einstein first proposed that light
consists of discrete units of energy known as photons: this dual nature of
light became known as the wave–particle duality. Louis de Broglie extended
the wave–particle duality principle to electrons. He argued that electrons
have both particle and wave features and proposed an equation that ex-
presses the wavelength of an electron beam as:39
l ¼ h/p (1.1)
where l is the de Broglie wavelength of electron, h is the Planck’s constant,
and p is the electron momentum. When comparing the wavelength of
electron waves to the wavelength of a visible light beam that is used in
optical microscopes, the wavelength associated with the electron is much
shorter than the wavelength of visible light. The average wavelength of
visible light is equivalent to 5000 Å, while the wavelength of electron rays
only reaches 1 Å. The discovery of the wave property of electrons is con-
sidered a new starting point for the invention of microscopes that rely on
electron waves, instead of using visible light rays. This led to much larger
magnification power, due to the very short wavelength of electron waves. The
magnification power of electron microscopes can reach up to 2.5 million
times enhanced magnification of a sample, which enables viewing at the
atomic or molecular level. The invention of electron microscopes created an
important and useful tool for studying and analyzing very small particles in
the nanoscale. Mentioned below are some of the electron microscope types
that are widely used in studies of nanoscale materials and structures.39,40

1.5.1 Transmission Electron Microscope

The development of magnification devices which rely on the use of electron
beams instead of visible light rays have had a great impact on the develop-
ment of nanoscience and nanotechnology. A transmission electronic
microscope (TEM) is one of the most important magnification devices used
in this field. It is a form of microscope that magnifies via the interaction of
electron beams passing through a sample. From there, an image can be
obtained on a fluorescent screen or by using a charged-coupled device (CCD)
camera. The ability of a TEM to magnify with high accuracy is due to the
short wavelength of electrons. This made the device a very important ana-
lytical tool used in nanomaterial research. The first TEM was built in 1938
Nanotechnology and Chemistry 13

Figure 1.11 An image of magnetite (Fe3O4) nanoparticles obtained by transmission

electron microscope (TEM).

and contained an internal vacuum system and electromagnetic lenses. The

TEM vacuum system enabled electron rays to reach the sample without
colliding with gas molecules while the electromagnetic lenses made of
magnets directed the electron path.40 Figure 1.11 presents an image of Fe3O4
nanoparticles obtained by a TEM.

1.5.2 Scanning Electron Microscope

A scanning electron microscope (SEM) is a device which can obtain three-
dimensional images for analyzing morphology and shape. The SEM shines
electron rays onto a sample and a three-dimensional scan of the sample is
obtained via mapping detailed information from the sample cavities,
scratches, and cracks. A magnetic field is used to control the movement of
the electron beam over the sample. The electron beam carries large amounts
of kinetic energy, but this energy disperses as a variety of signals generated
by electron-sample interactions when the electrons are slowed in the solid
sample.40

1.6 Nanoparticle Behavior in Colloid Solutions

Chemically, substances are divided into two main categories: (i) pure
substances, which includes elements and compounds; and (ii) mixtures.
Mixtures can be homogeneous or heterogeneous. In general, solutions
which are defined as homogeneous mixtures are uniform in composition.
Figure 1.12 presents three solutions that seemingly look the same. Solution