Nano-Chemistry

CHEM-7209
Dr. Rana Rashad
Nanotechnology

Nanotechnology is defined as the manipulation and control of matter at the

nanoscale, typically between 1 and 100 nanometers (nm).

The term nanotechnology refers to a branch of applied science and technology whose
unifying theme is the control of matter at the atomic and molecular scale, normally 1–
molecular scale

100 nm (1 nm = 10−9m), and the fabrication of devices within that size range.
 continued
• The nanotechnology is a multidisciplinary science, which combines chemical and
material engineering, biotechnology and industrial processing technology.
• It also plays an active role in trying to solve problems such as preservation and
food packaging (Cartelle and Zurita, 2015).
• As a general definition, Martín-Gago et al. (2009) described nanotechnology as
“the manufacture of materials, structures, devices and functional systems
through control and assembly of matter at nanometre scale, and the application
of new concepts and properties that arise as a result of a scale so small”.
• However, there are other definitions which are more widely used and accepted,
such as The Royal Society and The Royal Academy of Engineering (2004), which
defined it as “the design, characterisation, production and application of
structures, devices and systems by controlling shape and size at nanometre scale.
 Continured
• At these scales, materials often exhibit physical, chemical,
optical, and electronic properties that differ dramatically from
their bulk counterparts due to quantum confinement effects and a
very high surface-to-volume ratio
• The term "nano" is derived from the Greek word "nanos," meaning
"dwarf," which emphasizes the extremely small size of these
materials.
• It merges top-down (miniaturizing bulk materials) and bottom-up
(assembling atoms/molecules) approaches, bridging disciplines like
physics, chemistry, biology, and engineering.
 Nanoscale Unit
• Nanometer (nm): A nanometer is one-billionth of a meter,
or 1 nm=10−9 m
• This unit is commonly used to measure things at the nanoscale, such
as nanoparticles and biological molecules.
Centimeter 1×10−2 m
Millimeter 1×10−3 m
Micrometer 1×10−6 m
Nanometer 1×10−9 m
Angstrom 1×10−10 m
 Nanometer
• A nanometer (nm) is a unit of length in the metric system that equals one-
billionth of a meter (10⁻⁹ meters).
• It is used to measure objects and phenomena at the nanoscale, which
refers to dimensions typically between 1 and 100 nanometers.
• To understand how small this is, here are detailed comparisons and
examples:
• A nanometer is 1 nm=10−9 m, or one-billionth of a meter.
• The standard abbreviation for nanometer is nm.
Relation to Other Units:
• 1 micrometer (µm) = 1,000 nanometers.
• 1 millimeter (mm) = 1,000,000 nanometers.
continued
Real world examples of nm measurements
• A human hair is about 80,000 to 100,000 nanometers wide,
highlighting the minuscule dimensions involved in nanotechnology.
• Fingernails grow at a rate of about 1 nanometer per second, which
translates to approximately 86,400 nanometers in a day.
• The diameter of a strand of DNA is 2.5 nanometers.
• The size of a water molecule is approximately 0.2 to 0.5 nanometers.
• Many viruses fall within the nanoscale range; for example, the SARS-
CoV-2 virus (which causes COVID-19) measures about 60 to 120
nanometers in diameter.
 continued
• Common bacteria are generally between 1,000 and 10,000 nanometers in
size
• The diameter of a red blood cell is about 7,000 nanometers.
• The size of most atoms ranges from about 0.1 to 0.5 nanometers
• A single gold atom is approximately one-third of a nanometer in diameter
• These cylindrical structures can be around 1 nanometer in diameter but
can be much longer
• At the nanoscale, materials can demonstrate enhanced strength, lighter
weight, increased electrical conductivity, and greater reactivity compared
to larger-scale materials. These properties arise due to quantum
mechanical effects and a higher surface area-to-volume ratio.
 Historical Context
• 1959: Richard Feynman’s lecture, “There’s Plenty of Room at the Bottom”, envisioned atomic-scale
engineering.
• Direct manipulation of individual atoms for chemical synthesis

• Storing all the world's books in a small cube

• Building tiny motors and machines (swallowing doctors)

• Machines that could self-replicate on a smaller scale
• Feynman also expressed these thoughts and questions in his lecture
• "I don’t know why this hasn’t been done yet!“

• "What good would it be to see individual atoms distinctly?"

• 1980s: Invention of scanning tunneling microscopy (STM) and atomic force microscopy
(AFM), enabling nanoscale visualization/manipulation.
• 1985: Discovery of fullerenes (C₆₀), followed by carbon nanotubes (1991) and graphene
(2004), catalyzing modern nanotechnology.
 Why is the Nanoscale Special?
• At the nanoscale, materials often exhibit unique properties that
differ from their larger-scale counterparts. These differences arise
because:
• Increased Surface Area: As particles become smaller, their
surface area relative to their volume increases. This means more
atoms are exposed on the surface, which can enhance chemical
reactivity and affect physical properties.
• Quantum Effects: At this scale, quantum mechanical effects
become significant, influencing how electrons behave. This can
lead to changes in optical, electrical, and magnetic properties.
 Nanomaterials
• Nanomaterials are defined as materials that possess unique properties and
characteristics at the nanoscale, typically ranging from 1 to 100
nanometers (nm) in size.
• Types of Nanomaterials
1. Based on Dimensions
Zero-Dimensional (0D): Nanoparticles, quantum dots.
One-Dimensional (1D): Nanotubes, nanorods, nanowires.
Two-Dimensional (2D): Graphene, nanoplates, nanosheets.
Three-Dimensional (3D): Nanoflowers, nanostructured bulk materials.
2. Based on Composition
Carbon-Based: Fullerenes, carbon nanotubes (CNTs), graphene.
Metal-Based: Gold (Au), Silver (Ag), Titanium Dioxide (TiO₂), many others
Ceramic-Based: Oxides, silicates.
Polymeric Nanomaterials: Dendrimers, polymer nanocomposites.
 Based on Dimensions
• Every material in space has three dimensions: length, width, and height.
• If at least one of these three dimensions of a material is in the nanometer range,
the material is called a nanostructured material.
• To date, there is no comprehensive and universally accepted definition of
nanomaterials. However, the most accepted definition of nanomaterials is
provided by the US National Nanotechnology Initiative and is as follows
• Nanomaterials are a group of materials whose characteristic length scale is less
than 100 nm.
• Of course, some scientific reports may refer to materials with dimensions greater
than 100 nm as nanomaterials.
• Nanoscale is the size scale at which the properties of a substance differ from the
properties of the whole material (macroscale). One common category of
nanomaterials (nanostructures) is based on the number of dimensions outside
the nanometer range
 Continued
• According to this classification, nanomaterials are divided into three
categories: 0-dimensional, 1-dimensional, and 2-dimensional.
• If all three dimensions of a material are in the nanometer scale, the
material falls into the 0-dimensional nanostructure category.
• If two dimensions of a material are in the nanometer scale, the
nanostructure is 1-dimensional or If one dimension of a material
is outside the nanoscale (greater than 100 nm)
• If one dimension is in the nanometer scale, it is called a 2-dimensional
nanostructure or If two dimension of a material is outside the
nanoscale (greater than 100 nm)
 Continued
• Fig. 1 shows diagrams of zero-dimensional, one-dimensional, and
two-dimensional nanomaterials and images taken with an electron
microscope.
• Classification of nanomaterials based on their dimensions is one of
the most important categories. These three types of nanostructures
are significantly different from each other, not only in terms of
synthesis and manufacturing processes, but also in terms of
properties and applications
Figure 1
 Continued
• The electrical, optical, magnetic, surface properties, etc. of these three
nanomaterials are significantly different, so each has its own applications.
• For example, zero-dimensional, one-dimensional, and two-dimensional
nanomaterials have different abilities to absorb and emit light.
• A very important point when dividing nanomaterials by dimensions is that,
for example, for one-dimensional nanomaterials, it is not necessary that
only two dimensions are nanoscale, but it is possible to synthesize one-
dimensional nanomaterials that contain all three dimensions In these
nanomaterials, of course, one dimension must be many times larger than
the other two dimensions.
 Continued
• The situation is similar for two-dimensional nanomaterials: the other two
dimensions of these nanomaterials can also be nanoscale, but these two
dimensions must be much larger than the others.
• Fig. 2 shows images of one- and two-dimensional nanostructures taken with
a transmission electron microscope.
• Three types of nanostructures have been identified: zero-dimensional, one-
dimensional and two-dimensional, but apart from that, there are other
materials whose structure.
• Despite appearing as bulk materials (bulk means bulk materials, i.e.
dimensions of micrometers and above), is somehow nano-related and this is
what distinguishes them from non-nano-sized materials. We call these new
materials bulk nanostructured materials or 3D nanostructured materials.
Figure 2
 Continued
• For example, in the case of mesoporous materials, the dimensions of
the material are often much larger than nano, but they have nanoscale
pores
• It is worth mentioning that some researchers believe that the name
"nanostructure" should only be used for 3D nanostructured materials,
and only the word nanomaterial should be used for 0, 1 and 2D
materials.
 Zero Dimensional nanomaterials
• Zero-dimensional nanomaterials, also known as nanoparticles, are the
best-known nanostructures.
• Nanoparticles can have a variety of shapes: spherical, cylindrical, tubular,
cubic, hollow, core-shell, etc.
• However, most nanoparticles are spherical or irregularly shaped Fig.
3 shows some common shapes of nanomaterials
• Fig. 4 shows TEM images of spherical and polyhedral nanoparticles (zero-
dimensional nanostructures).
• The main reason for the greater use and popularity of zero-dimensional
nanostructures (nanoparticles) compared to one- and two-dimensional
nanostructures is the simpler synthesis method and lower cost of their
production.
Figure 3
 Grain Size
• In general, the properties of different materials/nanomaterials
strongly depend on the size of the grains, so to achieve uniform
properties throughout the material, the size of the grains should not
be too different in the microstructure and there should be a narrow
distribution of the grain size
• Fullerene is the most famous new zero-dimensional carbon
nanostructure .
• Fig. 5 shows the schematic of fullerene atomic structure and TEM
image of C60 fullerene.
Figure 4
Figure 5
 Examples of 0D materials
• This zero-dimensional nanostructure (fullerene) has 20 hexagons and 12
pentagons, and its structure is hollow.
• Another famous zero-dimensional nanomaterial are quantum dots (QD)
• Quantum dots are semiconductor crystals in nano dimensions (1–10 nm) that
consist of 200 to 10,000 atoms and their size is equal to the size of a large protein.
• Among the most common quantum dots, we can mention cadmium
selenide (CdSe) and cadmium sulfide (CdS)
• The new and main applications of quantum dots are
• Biological applications.
• Solar cells.
• Optoelectronic instruments.
• Photocatalytic applications
 Size and Properties
• In general, the various properties of quantum
dots, such as their optical properties, are strongly Size of
Emission Wavelength
dependent on their size. CdSe QD
• For example, research shows that the amount of
Color (nm)
(nm)
energy required to transfer electrons from the
valence layer to the conduction layer changes ~2 nm Blue ~470 nm
with the size of the quantum dots, and these dots ~3 nm Green ~520 nm
emit different colors depending on their size.
~4 nm Yellow ~550 nm
• CdSe is one of the most widely studied and ~5 nm Orange ~580 nm
used quantum dot materials. The emission
color changes depending on the size of the ~6 nm Red ~620 nm
QD:
 Quantum dots and Nanoclusters
• Quantum dots are very sensitive to the method and conditions of its synthesis,
and for this reason, their synthesis is done very carefully and under controlled
conditions.
• Among other zero-dimensional nanostructures, we can mention nanocluster.
• Nanoclusters are aggregates of atoms or molecules that typically less than 2nm.
• Nanoclusters contain a small number (several dozen) of atoms.
• These nanostructures can consist of one element or several different elements
and their size is usually less than 2 nm.
• Nanoclusters are usually made of metals and have attractive and unique
electronic, optical and chemical properties.
• According to another definition, nanoclusters are considered a bridge between
atoms and nanoparticles. Nanoclusters are used in medical and photocatalytic
applications Fig. 6 shows the structure of gold nanoclusters.
Figure 6
 One-dimensional nanostructures
• One-dimensional nanostructures are materials in which two dimensions are on
the nanometer scale and the other dimension is not on the nanometer scale; Or
all three dimensions are on the nanometer scale, so that one dimension is several
times larger than the other two dimensions.
• One-dimensional nanostructures are divided into three
categories, nanorods, nanowires, and nanotubes, depending on parameters such
as cross-sectional geometry and aspect ratio (the ratio of the largest dimension to
the smallest dimension).
• If the aspect ratio is small, it is a one-dimensional nanostructure of nanorods;
And if it is big, it is called a nanowire.
• If the cross-sectional geometry is spherical and hollow, it is called a nanotube.
• Fig. 7 shows the images taken with an electron microscope of one-dimensional
nanostructures.
Figure 7: Electron microscope images of one-dimensional nanostructures: (a) nanorod, (b) nanowire and (c) nanotube
 Continued
• The synthesis of one-dimensional nanomaterials is much more
difficult than the synthesis of zero-dimensional nanostructures.
• For this reason, their mass production is facing problems and in
commercial applications, especially applications in which there is a
need for a large volume of nanomaterials at a low price, they are used
less than zero-dimensional nanostructures.
• Nevertheless, due to the special properties of these nanostructures,
they are used in optical, electronic, etc.
 Examples and Properties of 1D Material
• Carbon nanotubes are one of the most famous and widely used one-dimensional
nanostructures.
• These nanostructures, like fullerene, are a new structure of carbon and are used
in many nanoelectronics devices due to their crystallographic structure and
unique properties.
• Due to its significant surface area, hollow structure, high mechanical strength,
excellent electrical properties, and the presence of unique structures in electron
bonds, this material is widely used in energy storage, nanocomposite materials,
and making nanoelectronics devices such as Nano sensors.
• Cytologically, carbon nanotubes are cylindrical tubes made of graphene sheets.
These materials can be made with one wall (Single-Walled Carbon Nanotube,
SWNTs) or multiple walls of tubular graphene sheets (Multi-Walled Carbon
Nanotubes, MWNTs).
• Fig. 9 shows a schematic of single-walled and multi-walled carbon nanotubes.
Fig. 9. Schematic of (a) single-walled and (b) multi-walled carbon nanotubes
 Two-dimensional nanostructures
• Two-dimensional nanostructures are divided into three
categories: thin film, nano sheet, and nano plate.
• Thin layers are more famous than the other two groups and have
wider applications. Usually, thin films are synthesized on different
substrates.
• Fig. 10 shows a diagram of the thin film along with their SEM and
AFM image.
• Due to having excellent properties such as optical properties and
resistance to corrosion and wear, thin films are used in various
industries such as making electronic and optical devices.
Fig. 10. A view of (a) the thin film along (b) their SEM image and (c) AFM image
 Graphene and its Properties
• Graphene is a two-dimensional sheet of carbon atoms in a hexagonal or
honeycomb pattern in which the atoms are connected by sp2 hybrids.
• Due to its unique properties, this material is used in the manufacture of
many delicate nanoelectronics and nanotechnology devices.
• The most important of these applications are electronic applications,
strengthening applications in composites, electro-optical applications,
medical engineering, targeted drug delivery and energy storage.
• In a graphene sheet, each carbon atom bonds with three other carbon
atoms.
• Graphene layers consisting of 3 to 10 layers are called "thin layer graphene"
and between 10 to 30 layers are called "thick multilayer graphene" or "thin
graphite nanocrystals" . Fig. 12 shows a diagram of graphite to graphene
conversion.
Fig. 12. Graphite conversion to graphene
 Nanocomposites
• A nanocomposite is a multiphase solid material where at least one of its phases has one,
two, or three dimensions measuring less than 100 nanometers.
• In simpler terms, it's a material made of two or more parts, and at least one of those
parts is incredibly tiny (at the nanoscale)
• Multiphase material is made up of multiple distinct components or phases
• The combination of these phases at the nanoscale leads to unique properties that are
different from the individual materials. Nanocomposites can have improved mechanical,
electrical, thermal, optical, electrochemical, and catalytic properties
• Examples of nanocomposites include ceramic matrix nanocomposites (CMNC), polymer
matrix nanocomposites (PMNC), and metal matrix nanocomposites (MMNC). These are
categorized based on the material that forms the main "matrix" of the composite
 Continued
• Imagine you're making a cake. The cake batter is like the "matrix"
material – it's the main stuff. Now, imagine adding tiny sprinkles (the
nanoparticles) that are super strong or have other special powers.
• When you bake the cake, the sprinkles are mixed in, making the whole
cake stronger, tastier, or even more colorful than it would be with just
the batter alone.
• That's what a nanocomposite is!
• It's a mixture of a regular material (the matrix) with extremely tiny
pieces (nanoparticles) that are less than 100 nanometers in size.
 Continued
• These tiny pieces make the whole material much better – stronger,
lighter, more conductive, or more resistant to heat or chemicals. They
don't need much of these tiny particles either, just a little can make a
big difference.
• The integration of nanomaterials into the proper matrix allows
exploiting a synergistic effect of the new nanomatrix which could
greatly improve the activity
 Porous material
• A porous material is a material containing pores, voids, or tiny holes within its structure. These
pores can be interconnected or isolated, and they can vary in size and shape. The skeletal part of
the porous material is often called the "matrix" or "frame".

• Pores: These are the voids within the material. To qualify a material as porous, the voids should be
accessible and permeable to fluids or gases

• Porosity: Porosity is the measure of the void space in a material and is a primary characteristic of
porous media

• Matrix: The solid part of the material, providing the structure

• Permeability: The ability of fluids or gases to pass through the interconnected pores

• High Surface Area: Porous materials generally have a high surface-to-volume ratio, which is
beneficial in applications like catalysis and filtration
 Porous Material
• Porous materials are classified based on several characteristics,
including pore size, pore structure, and porosity.
• The International Union of Pure and Applied Chemistry (IUPAC)
classifies pores into three main categories based on their width or
diameter
• Micropores: These are pores with size less than 2 nm. Some classifications further divide micropores
into narrow or ultramicropores (less than 0.7 nm) and supermicropores (0.7 to 2.0 nm).

• Mesopores: These pores have a size between 2 and 50 nm

• Macropores: These are pores have a size greater than 50 nm

 Continued
• Based on Pore Structure: Pores can also be categorized by their structure

• Open Pores: These pores are interconnected and allow fluids to pass through the material

• Closed Pores: These pores are isolated and do not connect with other pores.