Electrocatalyst and Electrocatalysis

An electrocatalyst is a catalyst that functions at the electrode surface or

most commonly may be the electrode surface itself.
It is a type of electrode material that interacts with specific species
during a Faradaic reaction but does not undergo any change.
Electrocatalysis is a heterogeneous catalysis which implies the reaction
occurs at the surface of the catalyst.
An effective electrocatalyst can exhibit high current density at low
overpotential.
Green hydrogen is the key to build up a carbon neutral society.
Electrocatalytic water splitting is a promising way to obtain green
hydrogen and a potential source of renewable energy.
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Fig: Conventional water electrolyzer
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A water electrolyzer consists of an electrolyte, anode and cathode.
Electrocatalysts for water splitting in acidic environment are IrO2 or
RuO2 for OER and Pt for HER.
When external voltage higher than equilibrium voltage is applied, HER
occurs at cathode yielding H2 and OER at anode yielding O2 gas.
A proton exchange membrane (PEM) is used to reduce loss in charge
transport.
In acidic solution,

Overall reaction:

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In alkaline medium,

Overall reaction:

The overall process requires an external voltage of 1.23 V corresponding to

an energy input of ∆G = 237.1 kJmol-1

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Catalysis for Energy and Environmental applications

Environmental catalysis covers the prime prospective for the reduction

of prime pollutants such as waste organic dyes, pesticides, toxic heavy
metals, chlorides, fluorides, COx, NOx, SOx and other organic and
inorganic compounds.
The composite material, activated carbon, bio-sorbent materials,
mesoporous materials, metal oxide nanoparticles, zeolites, nano
materials, metal organic frameworks (MOFs) appear to be promising in
the environmental remediation process.

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Catalytic conversion of fossil fuels

Catalytic conversion of fossil fuels to obtain hydrogen is the most viable

and economical technology.
It is thermodynamically favourable under atmospheric conditions.
Cost effective catalysts like Ni/Al2O3, Ni, Co, Cu can be efficiently
used.
To reduce carbon emissions, carbon capture can be done through
absorption, adsorption and membrane separation process.

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Hydrogen produced by water electrolysis or photocatalytic technologies is
called green hydrogen.
It is produced using renewable energy sources and the resulting hydrogen is
clean and emission free making it excellent choice for powering vehicles and
other applications that require a clean energy source.
It does not contribute to green house emissions and serve as a potential
alternative to fossil fuels providing a more sustainable source of energy for
future.

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Hydrogen obtained through reforming process using fossil fuels is called
grey (gray hydrogen).
It is carbon-intensive hydrogen as it produces significant amount of green
house emissions.
The technology for gray hydrogen is relatively well established and capable
of meeting requirements.
Catalytic conversion of fossil fuels can be performed by following four
methods:

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1. Steam reforming
It is a common method to produce hydrogen from natural gas and oil.
The process is represented as,

It is an endothermic process and the steam reforming of methane is by

far the largest source of hydrogen production.
But this process has highest amount of emissions.
The primary objective of this process is to produce safe, economical and
sustainable hydrogen economy.
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2. Partial oxidation (POX)
Catalytic partial oxidation of oil and hydrocarbons have been used for
hydrogen production in fuel cells for automobiles and other commercial
purposes.
It involves converting oil into hydrogen by combustion (partial
oxidation) with oxygen.

The high operating temperature and exothermic nature of reaction

makes the temperature control challenging.
This process also needs an expensive and complicated oxygen
separation unit to provide pure oxygen to the reactor.
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3. Pyrolysis
It involves the thermal decomposition of raw oil (absence of water or
oxygen) into hydrogen and carbon.

This process is beneficial as there is no need for secondary reactors as

well as there is significant reduction in emissions.
Some advantages are fuel flexibility, clean carbon by-product and a
decrease in CO and CO2 emissions.
One challenge is the fouling of catalyst due to carbon which can be
minimized by appropriate design.

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4. Autothermal reforming (ATR)
It involves adding steam to catalytic partial oxidation.

This process requires lower pressure.

Its advantage over steam reforming is its ability to start and stop while
producing a greater quantity of hydrogen than POX alone.
But for this process, the oxygen-to-fuel ratio and steam-to-carbon ratio
must be carefully controlled. Also it requires expensive oxygen
separation unit.

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Catalytic reduction of green house gas (GHGs) emissions

1. Reduction of non-CO2 GHGs

Catalytic combustion of methane can be carried out by partial oxidation,

dry reforming and steam reforming.
The catalysts used are similar to those used in catalytic conversion of
fossil fuels.
It offers economic benefits and avoids the formation of by-products like
formaldehyde.

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Catalytic control of N2O is challenging. Control technology includes
reuse of N2O from industrial emissions or catalytic decomposition or
reduction of emissions from power plants or waste.
Fe-ZSM-5 catalysts show good activity and selectivity in the reduction
of nitrogen oxides (NO, NO2, N2O) with oxygen and selective inorganic
or organic reducing agent.
Catalytic conversion of CFCs to fluorocarbons is best alternative to
control ozone layer depletion.
Pd on Al2O3 or C, AlF3 and various oxides show activity in processes
like hydrodechlorination, converting CFCs to HFCs
(hydrofluorocarbons)

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2. Reduction or conversion of CO2
CO2 is the major green house gas responsible for global warming and
climate change.
Study of CO2 conversion to chemicals and fuels like methanol is on the
rise.
Different approaches have been employed for utilization and conversion
of CO2 which have their own advantages and disadvantages.
Electrochemical approach- selectivity and activity high but lifespan of
catalyst is low and economically not feasible
Eg: sulphur modified copper catalyst converts CO2 into formate
Indium converts CO2 into acetate and formate

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Thermal approach- produces high yield but stability of catalyst is low
Eg: Ni converts it into methane
Photocatalytic approach- environmental friendly and economically
feasible but low product selectivity and less yield
Eg: reduction to methane and methanol in presence of TiO2 or ZnS
PET supported TiO2 converts CO2 into carbon monoxide
Biochemical approach- high selectivity and low operational temperature
and pressure but is costly and produce less yield
Chemo-enzymatic approach- produce bulk chemicals but require high
temperature affecting enzyme activity
Eg: nitrogenase reduce CO2 to methane
carbonic anhydrase reduce CO2 into bicarbonate
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Catalytic Dye Degradation

Organic dyes from industries contribute to environmental burden raising

ecological and health concerns in water bodies and also impart colour.
Treatment technologies like adsorption, coagulation, photocatalysis and
biodegradation are being implemented but wastewater containing dyes
have become one of the biggest challenges.
Catalytic degradation can transform organic compounds into less
harmful inorganic compounds.
Photocatalytic and biocatalytic dye degradation methods have gained
substantial attention.

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Photocatalytic dye degradation

It involves the attack and destruction of organic pollutants by reactive

species like hydroxyl species (OH˙) and holes (h+).
A variety of semiconductor materials have been used as photocatalysts
in treating organic pollutants.
The metal oxide NPs (like TiO2 nanoparticles) are excited upon
irradiation to generate electron-hole pairs, later forming photogenerated
carriers which interact with dye molecules to decompose into H2O and
CO2.
Commonly used commercial catalysts are TiO2, ZnO, SnO2, graphene-
gold nanocomposite and Ag-ZnO composite.

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The mechanism of catalytic dye degradation in presence of ZnO catalyst
is illustrated below:
i. activation of ZnO by UV light

ii. the redox reaction

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Biocatalytic dye degradation

Biocatalytic degradation through microbial reactions and use of

biodegradable enzymes is a crucial method for removing pollutants.
However their practical applications face numerous challenges like
stability, recyclability, catalytic efficiency etc.
Enzymes like peroxidases, lignin peroxidases, manganese peroxidases,
azo reductases, microperoxidase-11 and polyphenol oxidases are used as
catalysts in dye degradation.
Algae also plays significant role in dye degradation through biosorption
and biodegradation.

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Biosorption involves transfer of dye constituents from the liquid to solid
phase .
Biodegradation involves breaking the chemical bonds.
Various algal species like brown algae, green microalga have been
reported for their ability to biodegrade azo dyes like C.I. Basic Red 46,
Acid Red 27, Malachite green etc.

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