Question No.
1:
Different types of nanoparticles:
Nanoparticles can be classified into different types according to the size, morphology, physical
and chemical properties. Some of them are carbon-based nanoparticles, ceramic nanoparticles,
metal nanoparticles, semiconductor nanoparticles, polymeric nanoparticles and lipid-based
nanoparticles.
Carbon-Based Nanoparticles:
Carbon-based nanoparticles include two main materials: carbon nanotubes (CNTs) and
fullerenes. CNTs are nothing but graphene sheets rolled into a tube. These materials are mainly
used for the structural reinforcement as they are 100 times /stronger than steel.
CNTs can be classified into single-walled carbon nanotubes (SWCNTs) and multi-walled carbon
nanotubes (MWCNTs). CNTs are unique in a way as they are thermally conductive along the
length and non-conductive across the tube.
Fullerenes are the allotropes of carbon having a structure of hollow cage of sixty or more carbon
atoms. The structure of C-60 is called Buckminsterfullerene, and looks like a hollow football.
The carbon units in these structures have a pentagonal and hexagonal arrangement. These
have commercial applications due to their electrical conductivity, structure, high strength, and
electron affinity.
Ceramic Nanoparticles:
Ceramic nanoparticles are inorganic solids made up of oxides, carbides, carbonates and
phosphates. These nanoparticles have high heat resistance and chemical inertness. They have
applications in photocatalysis, photodegradation of dyes, drug delivery, and imaging.
By controlling some of the characteristics of ceramic nanoparticles like size, surface area,
porosity, surface to volume ratio, etc, they perform as a good drug delivery agent. These
nanoparticles have been used effectively as a drug delivery system for a number of diseases
like bacterial infections, glaucoma, cancer, etc.
Metal Nanoparticles:
Metal nanoparticles are prepared from metal precursors. These nanoparticles can be
synthesized by chemical, electrochemical, or photochemical methods. In chemical methods, the
metal nanoparticles are obtained by reducing the metal-ion precursors in solution by chemical
reducing agents. These have the ability to adsorb small molecules and have high surface
energy.
These nanoparticles have applications in research areas, detection and imaging of
biomolecules and in environmental and bioanalytical applications. For example gold
nanoparticles are used to coat the sample before analyzing in SEM. This is usually done to
enhance the electronic stream, which helps us to get high quality SEM images.
Semiconductor Nanoparticles
Semiconductor nanoparticles have properties like those of metals and non-metals. They are
found in the periodic table in groups II-VI, III-V or IV-VI. These particles have wide bandgaps,
which on tuning shows different properties. They are used in photocatalysis, electronics
devices, photo-optics and water splitting applications.
Some examples of semiconductor nanoparticles are GaN, GaP, InP, InAs from group III-V,
ZnO, ZnS, CdS, CdSe, CdTe are II-VI semiconductors and silicon and germanium are from
group IV.
Polymeric Nanoparticles:
Polymeric nanoparticles are organic based nanoparticles. Depending upon the method of
preparation, these have structures shaped like nanocapsular or nanospheres. A nanosphere
particle has a matrix-like structure whereas the nanocapsular particle has core-shell
morphology. In the former, the active compounds and the polymer are uniformly dispersed
whereas in the latter the active compounds are confined and surrounded by a polymer shell.
Some of the merits of polymeric nanoparticles are controlled release, protection of drug
molecules, ability to combine therapy and imaging, specific targeting and many more. They
have applications in drug delivery and diagnostics. The drug deliveries with polymeric
nanoparticles are highly biodegradable and biocompatible.
Lipid-Based Nanoparticles:
Lipid nanoparticles are generally spherical in shape with a diameter ranging from 10 to 100nm.
It consists of a solid core made of lipid and a matrix containing soluble lipophilic molecules. The
external core of these nanoparticles is stabilized by surfactants and emulsifiers. These
nanoparticles have application in the biomedical field as a drug carrier and delivery and RNA
release in cancer therapy.
Conclusion:
Thus, the field of nanotechnology is far from being saturated and it is, as the statistic says,
sitting on the staircase of an exponential growth pattern. It is basically at the same stage as the
information technology was in the 1960s and biotechnology in the year of 1980s. Thus it can
easily be predicted that this field would witness a same exponential growth as the other two
technological field witnessed earlier.
Question No.2
History of Nanotechnology:
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 ancient glass industry. It is the oldest famous example of dichroic
glass. Dichroic glass describes two different types of glass, which change color in certain
lighting conditions. This means that the Cup have two different colors: the glass appears green
in direct light, and red-purple when light shines through the glass.
(The Lycurgus cup. The glass appears green in reflected light (A) and red-purple in transmitted
light (B).
In 1990, the scientists analyzed the cup using a transmission electron microscopy (TEM) to
explain the phenomenon of dichroism.The observed dichroism (two colors) is due to the
presence of nanoparticles with 50–100 nm in diameter. X-ray analysis showed that these
nanoparticles are silver-gold (Ag-Au) alloy, with a ratio of Ag:Au of about 7:3, containing in
addition about 10% copper (Cu) dispersed in a glass matrix. The Au nanoparticles produce a
red color as result of light absorption (~520 nm). The red-purple color is due to the absorption
by the 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 nanomaterials. A similar effect is seen in late medieval church windows,
shining a luminous red and yellow colors due to the fusion of Au and Ag nanoparticles into the
glass. Figure shows an example of the effect of these nanoparticles with different sizes to the
stained glass windows.
(Effect of nanoparticles on the colors of the stained glass windows.)
During the 9th–17th centuries, glowing, glittering “luster” ceramic glazes used in the Islamic
world, and later in Europe contained Ag or copper (Cu) or other nanoparticles. The Italians also
employed nanoparticles in creating Renaissance pottery during 16th century. They were
influenced by Ottoman techniques: during the 13th–18th centuries, to produce “Damascus”
saber blades, cementite nanowires and carbon nanotubes were used to provide strength,
resilience, and the ability to hold a keen edge. These colors and material properties were
produced intentionally for hundreds of years. Medieval artists and forgers, however, did not
know the cause of these surprising effects.
In 1857, Michael Faraday studied the preparation and properties of colloidal suspensions of
“Ruby” gold. Their unique optical and electronic properties make them some of the most
interesting nanoparticles. Faraday demonstrated how gold nanoparticles produce different-
colored solutions under certain lighting conditions.The progression in nanotechnology due to the
blessings of nanoscience
Modern Era of Nanotechnology:
There was a progress in nanotechnology since the early ideas of Feynman until 1981 when the
physicists Gerd Binnig and Heinrich Rohrer invented a new type of microscope at IBM Zurich
Research Laboratory, the Scanning Tunneling Microscope (STM). The STM uses a sharp tip
that moves so close to a conductive surface that the electron wave functions of the atoms in the
tip overlap with the surface atom wave functions. When a voltage is applied, electrons “tunnel”
through the vacuum gap from the atom of the tip into the surface (or vice versa). In 1983, the
group published the first STM image of the Si(111)-7 × 7 reconstructed surface, which
nowadays can be routinely imaged.
(STM image of the Si(111)-7 × 7 reconstructed surface showing atomic scale resolution of
the top-most layer of silicon atoms.)
A few years later, in 1990, Don Eigler of IBM in Almaden and his colleagues used a STM to
manipulate 35 individual xenon atoms on a nickel surface and formed the letters of IBM logo.
The STM was invented to image surfaces at the atomic scale and has been used as a tool with
which atoms and molecules can be manipulated to create structures. The tunneling current can
be used to selectively break or induce chemical bonds.
(35 Xenon atoms positioned on a nickel (110) substrate using a STM to form IBM logo.)
In 1986, Binnig and Rohrer received the Nobel Prize in Physics “for their design of the STM”.
This invention led to the development of the atomic force microscope (AFM) and scanning
probe microscopes (SPM), which are the instruments of choice for nanotechnology
researchers today. At the same time, in 1985, Robert Curl, Harold Kroto, and Richard Smalley
discovered that carbon can also exist in the form of very stable spheres, the fullerenes or
buckyballs . The carbon balls with chemical formula C60 or C70 are formed when graphite is
evaporated in an inert atmosphere. A new carbon chemistry has been now developed, and it is
possible to enclose metal atoms and create new organic compounds. A few years later, in 1991,
Iijima et al. observed of hollow graphitic tubes or carbon nanotubes by Transmission Electron
Microscopy (TEM) which form another member of the fullerene family.The strength and
flexibility of carbon nanotubes make them potentially useful in many nanotechnological
applications. Currently, Carbon nanotubes are used as composite fibers in polymers and beton
to improve the mechanical, thermal and electrical properties of the bulk product. They also have
potential applications as field emitters, energy storage materials, catalysis, and molecular
electronic components.
(Schematic of a C60 buckyball (Fullerene) (A) and carbon nanotube (B).
C-dots:
In 2004, a new class of carbon nanomaterials called carbon dots (C-dots) with size below 10 nm
was discovered accidentally by Xu et al. during the purification of single-walled carbon
nanotubes .C-dots with interesting properties have gradually become a rising star as a new
nanocarbon member due to their benign, abundant and inexpensive nature. Possessing such
superior properties as low toxicity and good biocompatibility renders C-dots favorable materials
for applications in bioimaging, biosensor and drug delivery.Based on their excellent optical and
electronic properties, C-dots can also offer exciting opportunities for catalysis, energy
conversion, photovoltaic devices and nanoprobes for sensitive ion detection .After the discovery
of “graphene” in 2004, carbon-based materials became the backbone of almost every field of
science and engineering.
In the meantime, nanoscience progressed in other fields of science like in computer science, bio
and engineering. Nanoscience and technology progressed in computer science to decrease the
size of a normal computer from a room size to highly efficient moveable laptops. Electrical
engineers progressed to design the complex electrical circuits down to nanoscale level. Also,
many advances are noticed in smart phone technology and other modern electronic devices for
daily uses.
Conclusions:
The progress of nanoscience and nanotechnology in different fields of science has expanded in
different directions, to observe things from micro to nano, to even smaller scale sizes by
different microscopes in physics, from micro size bulk matter to small size carbon dots in
chemistry, from room size computers to mobile slim size laptops in computer science, and to
observe deeply the behavior of the cell′s nucleus to study single complicated biomolecules at
the nano level in biological science. All these progressions in different fields of science have
been generally overviewed and summarized in Figure
(Progress in nanoscience and nanotechnology in different fields of science.)
Question No.3
Properties of nano-oxides:
At present, nanoparticle research is an area of intense scientific activity due to a variety of
potential applications in several fields.The electronic structure of nanoparticles can reveal
semiconductor, metallic, or insulator character. The unique chemical and physical properties of
MONPs are attributed to the high density and limited size of corners and edges on their surface.
Potential technological applications of metal oxide nanoparticles play a vital role attracting
researchers with considerable interest from the fields of materials chemistry, medicine,
agriculture, information technology, biomedical, optical, electronics, catalysis, environment,
energy, and sense. Changes in cell parameters due to the size-related structural alterations
have been observed, for example, in nanoparticles of CuO, ZnO, SnO2, Al2O3, MgO, ZrO2
AgO, TiO2, CeO2, etc. As the size decreases in the nanoparticles, an increasing number of
surface and interface atoms generates strain or stress and adjoining structural
perturbations .The specific size of the nanoparticle can alter magnetic, conducting, chemical,
and electronic properties.
Magnetic metal oxidesnanoparticles;
have gained particular interest as their properties can be tuned based on their size and shape.
Magnetic, electronic, and chemical properties of nanoparticles can be dependent on a specific
size of the nanoparticle material.
Iron oxides: precisely magnetite, are of particular interest to materials scientists as they are
connected through series of potential applications, extending from magnetic storage devices
(MSD) to magnetic resonance imaging (MRI) contrast agents. Size-dependency was detected
in γ-Fe2O3 nanoparticles, where 55 nm particles exhibit ferromagnetic behaviour, while 12 nm
nanoparticles exhibit superparamagnetic behaviour without hysteresis .The decrease in particle
size will also decrease the total magnetic anisotropy while inducing the change to
superparamagnetic. Innovative easy methods of creating required sized metal oxide
nanoparticles are essential for attaining all the desired magnetic, electronic, and chemical
properties.
Electrical properties (conductance) are strongly dependant on the size of these particles
especially using oxides like SnO2, WO3, and In2O3 in gas sensing applications. Electrical/ionic
conductivity is a property of TiO2 materials that modulates to find practicality in the area of
sensors, optoelectronics, or photovoltaics. TiO2: can be easily reduced at high temperatures,
and this assertively impacts conductivity.One-dimensional (1-D)
Zno: engaged in both optoelectronic and electronic applications with wurtzite-type structure has
tremendous potential in applications from gas sensors to varistors. The long-range effects of the
Madelung field, present in the electronic properties of a bulk oxide surface, are either limited or
not present in the nanostructured oxide
Germania (GeO2) nanoparticles:
have many prospective applications for enhancing optical fibres and other optoelectronic fields.
Ga2O3 nanoparticles are also used in surface-catalysed systems for new electronic or optical
applications specifically at low temperatures. As a material with wider bandgap, it provides a
broad range of light emission; β-Ga2O3 is presently being investigated to exploit its potential for
optoelectronic applications. As known, the reduced-size nanoparticle enhances the chemical
reactivity due to its larger surface area to unit mass ratio.
Cuo:
nanoparticles are used in the microwave irradiation process, also as redox catalyst as well as a
catalyst in several oxidation processes, in photoconductive and photothermal applications.
MgO:
nanoparticles are extensively applied in various types of chemical industries as a material for
scrubber in eliminating gaseous air pollutants (CO2, CO, NOx, SOx) and also as a catalyst in
organic synthesis.
Al2O3:is used as a support for active phases in the area of catalysis coated with other
materials.
ZrO2:nanoparticles are exploited in structural ceramics, as a solid electrolyte, as a catalyst,
and also as gas sensing materials
CeO2:nanoparticles are used in areas of catalysis, gas sensing, electrochemistry, biomedical,
and material chemistry.
TiO2: nanoparticles are applied in various kinds of industrial applications related to
photocatalysis for pollutant elimination, solar cells, and also in material science and engineering.
ZnO: is a wide bandgap semiconductor material extensively studied for its intrinsic properties
but with limited industrial use as a UV-blocker in sunscreen creams and lotions, mixed varistors,
solar cells, partially as laser sources, optoelectronics, in gas sensors, and also as catalysts for
numerous types of organic reactions.
Conclusion:
All the listed properties and applications of certain MONPs described in the previous sections
are closely related to the structure, size, and shape of the nanostructures. It is clear that a large
number of factors will influence the structural characteristics and main properties of the
functional devices which will affect their performance. When combining two different nano-
oxides including the development of p–n junction or modifying them with a dopant, elaboration
of a nanostructure with optimal optical or electronic properties becomes a complex task.
Moreover, the suitable method for fabrication MONPs with tunable structural parameters and
properties should include optimization of all process parameters which could result in adverse
alteration of the obtained characteristics. The existence of such a large number of factors
influencing the structural characteristics and performance of the functional devices results in
difficulties in reproducing the results obtained.
Sources:
https://link.springer.com/article/10.1007/s42452-019-0592-3#:~:text=Properties%20of%20nano
%2Doxides&text=Magnetic%20metal%20oxides%20nanoparticles%20have,the
%20nanoparticle%20material%20%5B10%5D.
https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6982820/
https://www.azonano.com/article.aspx?ArticleID=4938
