The application of carbon nanotubes (CNTs) as metal-free catalysts

is a novel approach for heterogeneous liquid phase catalytic

systems. The performance of any catalyst depends on the
availability of suitable active sites,capable of chemisorbing the
reactants and forming surface intermediates of adequate strength.
Therefore, the surface chemistry of CNTs plays an important role on
the catalytic performance of CNTs for different applications. The
graphitic structure of the CNTs contains unsaturated carbon atoms
at the edges of the graphene layers as well as defects on the basal
plane. Both, contribute to the high the carbon surface with O-/N-/S-
containing compounds, allowing the incorporation of different
functionalities bound to the edge of the graphene layers, extending
the application of the CNTs to a wide range of processes.
Although at an early stage of research, CNTs supported metal-
nanoparticle catalysts as transition metals Ru, Co, Ag, Pt, Pd, and Au
shed new light to catalysis reactions in many fields such as
batteries, flat panel displays, and chemical sensors. In organic
synthesis like Heck reaction or Fischer–Tropsch synthesis, CNTs
supported Pd or Co catalysts are applied to improve catalytic
activity or to optimize experimental conditions. For the selective
catalytic reduction of NOx with hydrocarbons, CNTs supported Pt–
Rh catalyst displays higher NOx reduction activity.

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Carbon nanotube-supported Pd catalyst

1. In the catalysts of Heck reaction, precious metal Pd was the

most used active component. Supported Pd catalysts displayed
many advantages. Compared with the traditional homogeneous
Pd(OAc)2, PdCl2 catalysts in Heck reaction, CNTs-supported Pd
catalyst has higher catalytic activity, better stability, easier
separation and more satisfactory reusability.
Heck reaction

2. Catalytic hydrogenation of CO2 to produce methanol has been

considered as one of the most economical and effective ways to
chemically fix huge amount of emitted CO2 and also to improve
climate conditions. CNTs supported Pd catalyst has
considerable activity and selectivity, which is favored in
hydrogenation of CO2.

Carbon nanotubes supported Pt catalyst

As a kind of electrocatalyst support, CNTs have shown better

corrosion-resistance than other catalyst supports such as carbon
black under operational conditions. Besides, CNTs not only enjoy a
highly electrochemically accessible surface area but can also offer a
remarkable electronic conductivity due to its multi-wall structure,
which properties render it a competitive electrocatalyst support for
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Pt-catalyst. It has been found that the electrochemical activity of
different Pt-catalysts follows the order of Pt-WO3/CNT > Pt-Ru/E-
TEK-Vulcan > Pt/CNT > Pt/E-TEK-Vulcan > bulk platinum. The
reason why CNT based materials have higher electrochemical
response is most probably due to its higher surface area that are
electroactive.
Carbon nanotubes supported Co nanoparticles catalyst

Using carbon nanotubes as Co catalyst support was found to

decrease the temperature of cobalt oxide species. The strong metal-
support interactions are reduced greatly and the reducibility of the
catalysts improved significantly. CNTs help to increase the
dispersion of metal clusters and thus decreasing the average cobalt
clusters size. Research showed that the hydrocarbon yield obtained
by inventive CNTs supported Co catalyst is considerably larger than
that obtained from Co on alumina supports.

Schematic of CNT-supported catalyst

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The use of graphene-based materials in the field of catalysis has
attracted the interests of researchers in the last few years. Due to its
extremely high surface area and adsorption capacities, graphene is
expected to function as an excellent catalyst support material. The
interest is due to the activity and stability of grapheme based
catalysts through tailoring its structures/morphologies, catalytic
performance, and design for synthesis, catalytic mechanisms.
Graphene as a Carbocatalyst
Graphene is a one-atom-thick planar sheet of sp2 bonded carbon
atoms that are densely packed in a honeycomb crystal lattice.
Graphene based materials such as graphene oxide (GO) are
considered as a new class of carbocatalysts and opened a series of
novel application possibilities in chemical synthesis. Numerous
transformation, including the oxidation of alcohols and alkenes into
their respective aldehydes and ketones, as well as the hydration of
alkynes have carried out using grapheme as a carbocatalyst.
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It is observed that the GO with myriad oxygen atoms on its surface
can function as an efficient oxidant during anaerobic oxidation and
undergo reduction at the end of the first catalytic cycle. Moreover,
reduced graphene oxides with its residual oxygenated species
continue to activate molecular oxygen during aerobic oxidation.
The use of graphene materials in various catalytic applications,
including the oxidation of sulfides and thiols, C–H oxidation,
Claisen–Schmidt condensation, polymerization of various olefin
monomers, ring opening polymerization of various cyclic lactones
and lactams, and dehydration polymerization in the synthesis of
carbon reinforced poly (phenylene methylene) composites.
Graphene in Photo-catalysis

Another important application of graphene based materials that are

in photo-catalysis. Various reactions, including degradation of
pollutants, selective organic transformations and water splitting to
clean hydrogen energy were accomplished using graphene as a
photo-catalyst. GO can be hybridized with organic dyes or
organocatalysts to facilitate the photosensitization through charge
transfer across the graphene interface to produce synergistic effects
that enhance catalytic conversion. graphene as an electron-transfer
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medium.It was demonstrated that the graphene can store and
transport the electrons through a stepwise electron transfer
process.
Graphene as a Catalyst Support
In addition to their activity as a carbocatalyst, graphene based
materials are widely used as supports for catalytically active
transition metals. Owing to their extremely high specific surface
area which improves the dispersion of the catalytic metals,
improved chemical and electrochemical stability at operation
temperatures, enhanced electronic conductivity, grapheme based
materials are appealing choice as catalyst support. gold
nanoparticles (Au NPs) dispersed on graphite oxide were able to
catalyze methanol oxidation.
It is demonstrated that gold nanoparticles (Au NPs) dispersed on
graphite oxide were able to catalyze methanol oxidation.

It is demonstrated that the GO nanosheets not only serve as

structural components of the multilayer thin film, but also
potentially improve the utilization and dispersion of Au NPs by
taking advantages of the high catalytic surface area and the
electronic conduction of graphene nanosheets.
REFRANCE-:
1. Applications of Graphene in Catalysis. Lonkar and Abdala, J
Thermodyn Catal 2014, 5:2 DOI: 10.4172/2157-7544.1000132
2. Application of modified CNTs with TiIJSO4)2 in selective
oxidation of dimethyl ether. DOI: 10.1039/c6cy01367h
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