Baku State University

Nanochemistry

Lectures 4-5-6
Group of Carbon.

Lecturer: Dr. Elvin Y. Malikov

Baku 2023
 Baku State University/Nanochemistry/Lectures 4-5-6/Group of Carbon/Dr. Elvin Y. Malikov 2

Carbon is very significant element in nanotechnology. This element is the basis for organic and
inorganic substances, thus for the living and lifeless world. The backbone of the polymers is also
composed of the atoms of carbon element.
Generally, carbon atoms can form strong bonds between each other. Carbon atoms can form single,
double and triple bonds between each other which allow them to exist in different allotropic forms.
Mainly, carbon can be found as the allotropic forms in the nature. The most found forms are
diamond and graphite. It is obvious that the most stable form is graphite. Therefore all of the allotropic
forms sooner or late transforms to graphite. But, this is very slow process that takes centuries to be
completed. The simplest process is the transformation of the graphite to diamond that needs high pressure.
Later it was found that there are several basic and derivative allotropic forms of carbon. Basic
forms are diamond, graphite, carbine, fullerene, carbon nanotubes, graphene and nanodiamond.

Figure 1. Allotropic forms of carbon:

Graphite (a), diamond (b), fullerene (c), nanotube (d), graphene (e)

FULLERENE
The existence of this type of carbon was first theoretically mentioned by Soviet chemists in 1973.
Fullerene consists of 60 carbon atoms. It resembles the soccer ball. It is an icosahedron consisting of the
20 hexagons and 12 pentagons.
In fullerene the distance between the center of icosahedron and carbon atom is 3.512 Å, the length
of the C-C bond in the hexagons is 1.45 Å, but in pentagons it is 1.40 Å. The length of the C=C double
bond isə 1.39 Å.
Classical fullerene is C60 (buckminsterfullerene). That is the sphere resembling the soccer ball
with 1 nm diameter. The sp2 hybridization of all the carbon atoms is characteristic for this cluster. This
structure retains its stability until 1700K temperature. It is gradually destroyed at the higher temperatures.
That`s why the temperature in the reactor for synthesis of fullerene should not exceed 1600-1700 K. C70
is the most common fullerene type after the C60 and it resembles a rugby ball.
In 1985 British and American chemists Robert Curl, Harold Kroto and Richard Smalley
synthesized brown-yellow substance (C60) by the laser evaporation of the graphite under vacuum. They
named this substance as buckyball. In 1996 they were awarded the Noble Prize for the invention of the
C60 and C70 fullerenes. Generally, the name of these nanostructures was an homage to Richard
Buckminster Fuller, whose geodesic domes it resembles. Fullerene is soluble in organic solvents (for ex.,
benzene). The C60 monocrystal can be grown by consequent solvation of the fullerene in benzene and
slow evaporation (this process can not be done with diamond, graphite and carbene). C60 spheres
(buckyballs) are very durable. They can endure 20 GPa strain.
 Baku State University/Nanochemistry/Lectures 4-5-6/Group of Carbon/Dr. Elvin Y. Malikov 3

Figure 2. C60 and C70 fullerenes

Figure 3. Buckminster Fuller and his invention-geodesic domes

Figure 4. Similarities between soccer ball and C60 struckture.

In fullerene all the carbon atoms are in saturated form. Surface carbon atoms in diamond, graphite
and carbene fill up their outer bonds with hydrogen, oxygen and so on. According to the Nuclear
Magnetic Resonance spectra fullerene does not possess this type of admixtures. Thus fullerene is the only
pure and stable form of carbon. The other fullerene structures (C20, C22, C70, C76, C80, C84, C240, C540, C960,
C1500, etc.) were also synthesized besides the C60 structure. Fulleren is very durable to the chemical
reagents. The strong oxidant like fluorine reacts with fullerene gradually. The product of this fluorination
is white C60F60.
Due to the electronegativity C60 fullerene can form C60H36, C60F36, C70F44 structures without
destruction.
 Baku State University/Nanochemistry/Lectures 4-5-6/Group of Carbon/Dr. Elvin Y. Malikov 4

Figure 5. The other fullerene types

Figure 6. Fullerene under Transmission electron microscope

Generally, fullerenes can form various derivatives with the interaction with metals, fluorine, etc.
Following fullerene types can be synthesized by chemical reactions:
 Endohedral fullerenes, also called endofullerenes, are fullerenes that have additional atoms, ions,
or clusters enclosed within their inner spheres

 Exohedral fullerenes, also called exofullerenes, are fullerenes that have additional atoms, ions, or
clusters attached their outer spheres, such as C50Cl10 and C60H8 or fullerene ligands
 Fullerene derivatives are the structures that are formed with replacement of the one or several
carbon atoms with other atoms.
The first endohedral fullerene (La@C60) was obtained in 1985 with laser evaporation of graphite
saturated with LaCl3. The common Exohedral fullerene (C60H2, C60H4, C60H18, etc.) is C60H1. Besides,
they have fluorinated derivatives (C60F18, C60F36, C60F48). The first fullerene derivative was C59B
synthesized by replacement of carbon atoms with boron. It was synthesized with laser evaporation of
boron nitride doped graphite.
 Baku State University/Nanochemistry/Lectures 4-5-6/Group of Carbon/Dr. Elvin Y. Malikov 5
The application of fullerenes is very wide so that they can be applied as the medicine against the
viral illnesses like flu, immune deficiency, ancological and neurodegenerative diseases, osteoporosis and
vessel diseases.
For instance, recent investigations show that C60 fullerenes doped with the radioactive elements
can be used as the drug delivery medicine for tumor diagnosis and treatment. But for this purpose the
surface of the doped fullerene should be decorated with the functional groups that allow this drug delivery
medicine to attach to the tumor cells.
Furthermore metal doped fullerenes can be used as the superconductors. 26% volume of the
fullerenes is cavity that can be filled with atoms of alkali metals. If the C60 crystals and metallic
potassium will be placed into the tube (with vacuum inside) and heated till 400˚C temperature, the
potassium vapors will occupy the cavity and transform the C60 to K3C60. C60 molecules are dielectric, but
they are converted to superconductors as the result of the dopping process with metals. C60-ethylene
structure shows ferromagnetic features.

Figure 7. Doped fullerenes

Fullerites. The fullerites are condensed systems composed of fullerenes. The C60 crystal is the
most studied fullerite, but the less studied one is C70 crystal. The difficulties in studying of the higher
fullerens is due to the hardship of their synthesis process. In fullerene molecule carbon atoms are
connected with each other with σ and π bonds. There is not any chemical bond between fullerene
molecules within the crystal. That`s why fullerene molecules keep their individuality within the
condensed system. There are van der Waals forces between molecules within the crystal.

Figure 8. Fullerite

GRAPHENE
Graphene is a two-dimensional allotropy of carbon in sp2 hybridized form. It is a two-dimensional
one layer thick hexagonal crystal lattice formed of the σ and π bonded carbon atoms. Generally, graphene
is a single layer of graphite.
 Baku State University/Nanochemistry/Lectures 4-5-6/Group of Carbon/Dr. Elvin Y. Malikov 6

Figure 9. Graphite and graphene

Ideal graphene consists of hexagonal centres. The distance between the nearest carbon atoms in its
crystalline structure is 0.142 nm. Formation of the pentagons and heptagons in graphene makes them
defected. Thus, pentagons make the conical shaped structures, but heptagons some saddle-like structures.
Technically it is difficult to synthesize the ideal graphene that consists of only hexagonal centres.
The interestig fact obtained by the investigations is that the rolling up the graphene sheets into the
cylinders yields the singlewalled carbon nanotubes and the rolling ways affect the properties of the
obtained nanotubes. Depending on the rolling direction they can be metallic or semiconducting materials.
In 2011 the employees of National Radio Astronomy Observatory mentioned the existence of
graphene in space.
The advantage of the graphene sheet in comparison to graphite is that, in graphene just 3 electrons
take part in a bonding process, but the 4th electron is free which is the main reason of the excellent
coductivity properties of the graphene (its resistance is 0.0014 Om·sm). Futhermore graphene shows high
mechanical strength (~1 TPa).
Graphene was discovered, isolated, and characterized in 2004 by Andre Geim and Konstantin
Novoselov at the University of Manchester. They were awarded the Nobel Prize for this invention in 2010.
The physical and chemical properties of graphene have not fully studied yet. But the results of the
preliminary investigations show that graphene has unique properties and can be widely applied. Graphene
shows high mechanical and thermoconducting properties. This material seems to be a future of the
nanoelectronics.
Graphene can also be used as the sensors for definition of various chemicals. Working principle of
these type of sensors is simple. Since molecules of some substances are electron donors and the others are
electron acceptors they can change the resistance of the graphene in different manner. That changes can
be used as the analytical signals for identification of the molecules. Futhermore graphene can be used as
an electrode in ionistors (supercapacitors).

NANODIAMOND
Nanodiamonds or diamond nanoparticles are diamonds with a size below 1 micron. They can be
produced by impact events such as an explosion or meteoritic impacts. They are the nearest to natural
structures than other nanoforms of carbon.
In 1963, Soviet scientists noticed that nanodiamonds were created by nuclear explosions that used
carbon-based trigger explosives.
It is obvious that natural diamond is crystalline structure with excellent hardness. All of the carbon
atoms in diamond is in sp3 hybridized state and each carbon atom forms single bond with its 4 adjacent
carbon atom. Because of the expenditure of all valence electrons of carbon atom in formation of the
structure, diamond is dielectric material.
The difference between natural and nanosized diamond is not just in size (the size of nanodiamond
is ~ 2-4 nm), but also in the placement of the most carbon atoms on the surface which gives them
advanced properties.
 Baku State University/Nanochemistry/Lectures 4-5-6/Group of Carbon/Dr. Elvin Y. Malikov 7

Figure 10. The appearance (above images) and the Transmission Electron Microscopy images (below
images) of the Natural nanodiamond aggregates from the Popigai crater, Siberia, Russia.
Surface atoms have free valencies which make nanodiamons available to form pentagons and
hexagons like fullerenes. Thus, at room temperatures diamond nanoparticles consist of diamond core and
fullerene shell.

Figure 11. The image of the bulk (a) and nanosized (b) diamond

Nanodiamonds are very reactive due to the surface atoms. For example, at 1800˚C temperature
bulk diamond transforms to graphite, but in nanodiamond case this transformation proceeds at 1000˚C.
The oxidation of ordinary diamond proceeds in air at 900˚C, but nanodiamond at 450˚C.
Nanodiamonds are safe and healthy materials that make them available for biomedical and
mechanical applications. It is possible to chemically attach some medical substances onto the surface of
the nanodiamonds with 5 nm size in order to prepare drug delivery medicines. They can easily cross the
blood-brain barrier and prevent the stroke. In 2013 the ND-DOX drug was prepared by the chemically
attachment of the doxorubisin molecules (famous medicine for cancer) onto the surface of nanodiamond.
The investigations show that cancer cells can not reject this drugs and they fully influence the cells, but
the side effects are not observed.
Nanodiamonds are easily absorbed by the human skin. They can be used as the tool for absorbtion
of the ingredients of the skin protection products. Nanodiamonds can form strong bonds with water
molecules, therefore they can be used as the moisturizing agent for skin.
 Baku State University/Nanochemistry/Lectures 4-5-6/Group of Carbon/Dr. Elvin Y. Malikov 8
Nanodiamonds are also usefull in electronics. It is possible to produce sensors, optical and
quantum computers using this material.
CARBON NANOTUBE
A carbon nanotube is a tube-shaped material, made of carbon, having a diameter measuring on the
nanometer scale. Sidewalls of carbon nanotubes are composed of ideal hexagons. Hemisphere caps are
composed of pentagons.

The true identity of the discoverers of carbon nanotubes is a subject of some controversy. In 1952,
L.V.Radushkevich and V.M.Lukyanovich published clear images of 50 nanometer diameter tubes made
of carbon in the Soviet Journal of Physical Chemistry. This discovery was largely unnoticed, as the article
was published in Russian, and Western scientists' access to Soviet press was limited during the Cold War.
In 1991 Japanese scientist S.Iijima investigated the structure of the multi-walled carbon nanotubes.
There are several types of carbon nanotubes - single-walled or multi-walled, stright or spiral, long
or short, conductiong and semiconducting nanotubes and so on.
The graphene sheets can be rolled in different ways to get the three types of carbon nanotubes -
armchar, zigzag, chiral.
Depending on the diameter and chirality of the carbon nanotubes metallic (conducting) and
semiconducting carbon nanotubes are distinguished. The 2/3 of carbon nanotubes are semiconducting and
1/3 are metallic in the synthesized carbon nanotube mixture. Metallic nanotubes are mostly in armchair
structure. The results of the investigations prove that the band gap decreases with increasing of the
diameter of carbon nanotube.
Nanotubes show extraordinary tensile strength. They are not torn, cut, broken but change their
structures and self-organize under high mechanical strain.
Chemical properties of carbon nanotubes differ from the properties of fullerenes and graphene.
Fullerenes can form molecular crystals, graphite is complex polymeric crystal, but carbon nanotubes are
intermediate form between them. The hole inside the nanotube is much bigger than the hole of fullerene.
The nanochemistry of the carbon nanotubes deals with the functionalization of the sidewalls. The
modification of sidewalls of the nanotubes actively carried out through fluorination. The diameter and the
distance between sidewall layers are increasing through the fluorination which ends with the exfoliation.
Carbon nanotubes can be used as the matrix for synthesis of the metal nanoparticles.

Figure 12. Single-walled (A) and multi-walled (B) carbon nanotubes

 Baku State University/Nanochemistry/Lectures 4-5-6/Group of Carbon/Dr. Elvin Y. Malikov 9

Figure 13. Rolling up of graphene sheet into the carbon nanotubes

Figure 14. Types of Carbon nanotubes: zigzag (a), chiral (b) and armchair (c)
 Baku State University/Nanochemistry/Lectures 4-5-6/Group of Carbon/Dr. Elvin Y. Malikov 10
Synthesis of carbon nanostructures.
The main synthesis methods of the carbon nanostructures are listed below:
 Arc discharge of graphite;
 Laser ablation of graphite;
 Chemical vapor deposition method.
Arc discharge of graphite. This is widely used method and was first applied by S. Iijima in 1991.
The arc discharge is formed between graphite electrodes inside the chamber filled with inert gas (mainly
He or Ar). The cathode and the walls of a chamber are cooled by liquid nitrogen. Under the gas pressure
less than atmospheric, at 100 A arc current and 25-35 V voltage the temperature of the plasma formed
between electrodes reaches 4000 K. Graphite anode melts at this temperature. With sharp decrease of the
temperature carbon atoms move from the hot zone of the plasma to the cold zone and condense with
deposition on the chamber walls and cathode surface. Microscopic images show that the product contains
not only amorphous carbon (soot) and graphite, but also fullerene and carbon nanotubes. Thus the one
part of the yield (graphite, soot, fullerene) is deposited on the cold walls of the chamber, but the other part
(graphite, nanotube) on the surface of the cathode.
In this device the diameter of the electrodes is about 5-20 nm and the distance between them is 1
nm. For synthesis of the single-walled carbon nanotube Co, Ni and Fe are placed into the center of the
positive electrode as catalyst. Multi-walled carbon nanotubes are formed without the catalyst.

Figure 12. Scheme of the synthesis device of the carbon nanotubes with arc discharge method

The nanotubes with 1-5 nm diameter and 1 micron length can be obtained with arc discharge
method. But, changing the condition (gas type, pressure, distance between electrodes) can yield the
nanotubes with bigger diameter and length.
Laser ablation of graphite. This process was developed by Dr. Richard Smalley and co-workers
at Rice University, who at the time of the discovery of carbon nanotubes, were blasting metals with a
laser to produce various metal molecules. When they heard of the existence of nanotubes they replaced
the metals with graphite to create multi-walled carbon nanotubes. In this method the graphite evaporated
by laser is condensed on the cooled collector.
Graphite target is placed into the quartz tube inside the cylindrical furnace with temperature 1000-
1200˚C. The tube is purged with buffer gas (He or Ar) and the reaction is carried out under this gas
medium. The target is exposed to the laser beam (energy-140 mJoule, focus-1.6 mm, frequency-8 hs).
The product (very hot carbon cloud) is transferred from hot zone to cold zone and condensed on the
surface of the cooled collector. The content of the product is about 30-35% carbon nanotube, 20%
amorphous carbon, 12-15% fullerene, 12-15% carbohydrogens, 5-10% graphitized nanoparticles, 10%
catalyst particles (Co and Ni) and 1-2% silicon. The diameters of the nanotubes depend on the irradiation
power.
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Multi-wall carbon nanotubes are formed in the case of the pure graphite, but single-wall nanotubes
are formed from Co, Ni and Fe catalyst doped graphite. Actually bimetallic catalysts (Ni/Co, Ni/Fe,
Co/Fe, Pd/Pt) are used in this method and the content of the catalyst directly affects the efficiency of the
process. This method is feasible for the synthesis of the single-walled carbon nanotubes than the rest.
The disadvantage of this method is the low productivity and high cost. High amount of energy is
needed during the process.

Figure 16. The device for laser ablation of graphite

Chemical vapor deposition method. That is more practical and massive method in production of
carbon nanotubes. It is based on the thermochemical deposition of carbon-based gas over the hot surface
of the catalyst. Carbon-based gas mixture (usually the mixture of acetylene or methane with nitrogen)
purged through the quarz tube inside the furnace with temperature between 700-1000˚C. There is ceramic
crucible filled with the catalyst powder inside the quartz tube. As the result of the chemical reaction
between catalyst and gas atoms the carbohydrogen decomposition proceeds that makes possible the
process of the carbon deposition over the catalyst surface and formation of the carbon nanotubes and
fullerenes. The inner diameter of the obtained nanotubes is about 10 nm and the length can reach about
several microns. The geometrical parameters of the obtained nanotubes depends on the condition of the
process (time, temperature, pressure, type of the buffer gas), type of the catalyst and its dispersity.
Recently, synthesis of the carbon nanostructures using this method is intensively increased. The
efficiency of this method is high which makes it available for industrial use.
It is possible to synthesize the graphene from graphite using the chemical methods. The
microcrystals of graphite are treated with the mixture of sulfuric and hydrochloric acids. The graphite
oxidizes and carboxylic groups are formed at sides of the graphene structure. They are converted to
chlorides by thionylchloride. Then using the octadecylamine in tetrahydrofuran, tetrachloromethane and
dichloroethane solvents they are converted to graphene sheets with 0.54 nm thickness.
There are another two methods of graphene synthesis:
 Radiofrequency-plasma chemical deposition from gas phase;
 Highpressure and hightemperature growth method.
In all synthesis methods of carbon nanostructures the slag (soot, particles of amorphous graphite,
metal remnants from the catalyst) is formed which should be eliminated from the main product. Various
purification methods are used for cleaning of the product. For example, mechanical (filtration, sonication,
centrifugation) and chemical (rinsing with chemically active materials, heating, etc.) methods. The
investigations for development of economically advantageous methods are on progress.