KYAMBOGO UNIVERSITY

COURSE INFORMATION

Course Code & Name: MCH 7105, Advances in

Electrochemistry
Name Lecturer Dr. Justus Masa

PRESENTERS’ INFORMATION
KAAYA GODFREY
Reg. No. 20/U/GMCH/13338/WKD

COURSE: MASTERS OF SCIENCE IN

CHEMISTRY
 ELECTROCHEMICAL REDUCTION(VALORIZATION) OF CARBON DIOXIDE TO
FUELS AND CHEMICALS
Question
Electrochemical conversion of CO2 to fuels and chemicals is considered one of the most
appealing means for reducing our heavy reliance on fossil fuels for energy, which is detrimental
to the environment and is primarily responsible for global warming. Outline (briefly), with the
aid of chemical equations, at least five products that can be produced from electrochemical
reduction of CO2 and discuss, for each of the products, the current major challenges that have
to be overcome to realize this dream.
Introduction
CO2 can be converted to other chemicals by chemical, photochemical, electrochemical, and
photoelectrochemical methods, which break the C=O bond.
Electrochemical reduction of CO2 is a conversion of carbon dioxide to reduced chemical species
using electrolysis(electricity). It is a step commonly used in carbon capture and is possibly the
most effective way to convert CO2 into useful fuels by using efficient catalysts. We can equally
say that using the electrochemical method in the reduction of carbon dioxide to important fuels is
beneficial for the following reasons
✓ The high energy density of the produced fuel.
✓ The simplicity of the operation.
✓ The temperature conditions of the operation i.e., room temperature.
✓ The ease in controlling the process.
Electrochemical reduction of CO2 can proceed through two-, four-, six-, and eight-electron etc
reduction pathways in gaseous, aqueous, and nonaqueous phases at both low and high
temperatures. The major reduction products are carbon monoxide (CO), formic acid (HCOOH)
or formate (HCOO−) in basic solution, oxalic acid (H 2C2O4) or oxalate (C2O42− in basic solution),
formaldehyde (CH2O), methanol (CH3OH), methane (CH4), ethylene (C2H4), ethanol
(CH3CH2OH), as well as others.
Furthermore, researchers have found different electrodes and electrolytes that can be used in the
transformation of carbon dioxide into low carbon fuels. Some of the electrodes that can be used
are tin and copper-based materials whereas some of the electrocatalysts are noble metals,
transition metal-based nanostructure materials.
The following table summarizes the cathodic reactions for the production of various products

Chemical species Reaction Electrode

potential(V)
methanol CO 2 ( g ) +6 H +¿ (aq) +6 e→ CH OH (aq )+H
3 2 O (l )¿
-0.38

Ethanol 2 CO2 + 12 H+ + 12 e− → C2H5OH + 3 H2O −0.329

Ethylene 2 CO2 + 12 H+ + 12 e− → C2H4 + 4 H2O −0.349

Methane CO2 + 8 H+ + 8 e− → CH4 + 2 H2O -0.24

Carbon monoxide CO2 + 2 H+ + 2 e− → CO + H2O −0.53

Formic acid CO2 + 2 H+ + 2 e− → HCOOH −0.61

Oxalic acid 2 CO2 ( g ) +2 H +¿ (aq )+2 e→ H 2 C 2 O4 ( aq ) ¿ -0.48

The anode reaction in all the cases is the same as follows;

2 H 2 O ( l ) → O2 ( g ) + 4 H +¿ ( aq)+ 4 e¿

Attention to them is due to their several advantages;

✓ The process is controllable by electrode potentials and reaction temperature.
✓ The supporting electrolytes can be fully recycled so that the overall chemical
consumption can be minimized to simply water or waste water.
✓ The electricity used to drive the process can be obtained without generating any new CO 2
—sources include solar, wind, hydroelectric, geothermal, tidal, and thermoelectric
processes.
✓ The electrochemical reaction systems are compact, modular, on-demand, and easy for
scale-up applications
However, challenges remain like:
 ✓ The slow kinetics of CO2 electroreduction, even when electrocatalysts and high electrode
reduction potential are applied.
✓ The low energy efficiency of the process, due to the parasitic or decomposition reaction
of the solvent at high reduction potential.
✓ The high energy consumption. Researchers have recognized that the biggest challenge in
CO2 electroreduction is low performance of the electrocatalysts (i.e., low catalytic activity
and insufficient stability).
Electrochemical reduction of carbon dioxide to methanol
The following are electrode reactions:
+¿ ( aq ) + 4 e¿
Anode reaction: 2 H 2 O ( l ) → O2 ( g ) + 4 H
+¿ ( aq ) +6 e→ CH 3 OH ( aq ) +H 2 O (l )¿
Cathode reaction: CO 2 ( g ) +6 H

Overall redox equation: 2 CO2 ( g ) +4 H 2 O ( aq ) →2 CH 3 OH ( aq ) ( aq ) +3 O2 ( g )

The following are the challenges;
Carbon dioxide (CO2) can be converted to methanol (CH3OH) through different methodologies.
Most of them are in the research stage and are hot topics in catalysis domain. However,
electrochemical cells are preferred over other methodologies for conversion of CO 2 to methanol.
But several obstacles still persist in the CO2 electrochemical reduction which include:
➢ Several types of catalysts (homogeneous, heterogeneous, photo catalysts, electro catalysts
and biocatalysts) are been developed to play an important role in such processes.
However, CO2 is quite inert and its conversion is highly kinetically and
thermodynamically unfavorable, so it is of crucial importance to develop highly efficient
and selective catalysts. In heterogeneous catalysis for carbon dioxide reduction to
methanol, poor selectivity and low/high reaction are considered as major limitation. The
electro catalyst used in electrochemical reduction is should have higher selectivity for
methanol formation as well as lower over potentials. Many heterogeneous electro
catalysts are selective to methanol formation, fast and energy-efficient, but they are
unstable in nature.
➢ Further, the progress in electro catalytic reduction of CO 2 into methanol will originate a
facile and clean recycling process for CO2 that also aid to diminish the greenhouse effect.
Owing to the importance of methanol as a fuel, various sorts of materials can be
employed for the efficient electrochemical reduction of CO 2 to methanol. High methanol
selectivity can be easily achieved under low temperature operation (90%) while CO2
hydrogenation conversion is lower.
➢ Furthermore, the understanding of the CO2 reaction mechanisms (C-O, C-C and C-H
bonds formation), pathways and intermediates to generate useful products is still
insufficient, although the literature contains some attempts to understand the CO 2 electro
reduction process
 ➢ In addition, the estimation of the actual costs to produce CH 3OH via electrochemical
reduction of CO2 will require the development of in-depth cost and life cycle analysis
models. There are still several issues that need to be tackled for this technology.
➢ Finally, there is an important drawback on the technology of methanol production from
switch grass by capturing and hydrogenating CO 2 that is released in the production of the
syngas. The large amount of energy required leads to the need of large solar fields, wind
farms and biogas production facilities. There are only a number of feasible locations for
such an integrated facility
➢ However, the technology of CO2 electro reduction to methanol is still long way to go and
will probably become practical and economically feasible in the near future. In the future,
the electricity needed for electrochemical CO2 reduction process on a large scale could be
supplied from renewable energy sources like solar and wind farm, tidal electricity,
hydroelectricity etc. In future, researchers must work on fabricating new electro catalysts
that will allow working at high current densities without any loss in faradaic efficiency.
Electrochemical reduction of carbon dioxide to oxalic acid
The following are electrode reactions:

Anode reaction: 2 H 2 O ( l ) → O2 ( g ) + 4 H +¿ ( aq)+ 4 e¿

+¿ ( aq ) +2 e→ H 2 C 2 O4 ( aq ) ¿
Cathode reaction: 2 CO2 ( g ) +2 H

Overall redox equation: 4 CO2 ( g ) +2 H 2 O ( aq ) →2 H 2 C 2 O 4 ( aq ) +O2 ( g )

The following are the challenges
Until now, this topic has not been studied in great depth and there is no industrial application yet.
Oxalic acid has been overlooked as a potential promising product of the CO 2 reduction, mainly
because it particularly forms in non-aqueous solutions. In aqueous solutions, there is too much
competition with other electrochemical reduction reactions.
➢ For the electrochemical reduction of CO2 to oxalic acid, the high electricity consumption,
the low electrode stability and the difficult downstream processing are the main reasons
the process is not economically feasible yet.
➢ CO2 has a very stable, linear, symmetrical structure, which makes it non-polar. Due to the
stability, lots of energy is needed for the first (rate-limiting) step in the reduction, which
means that large overpotentials need to be applied.
➢ Using a catalyst could reduce the activation energy, however the non-polarity makes it
difficult to selectively adsorb CO2 on catalysts. If the CO2 reduction is performed in
aqueous solution, there is competition at the working electrode with the hydrogen
evolution reaction.
➢ In aqueous media, water is abundant compared to CO2, which favors the hydrogen
evolution reaction. The kinetics of HER (hydrogen evolution reaction) are also faster
compared to CO2 reduction and the both reactions occur in the same potential range. CO2
is also a relatively large molecule, which leads to slow mass transfer and limits the rate of
 reaction. Besides the low mass transfer, CO2 is poorly soluble in water, which is also a
factor why the reaction is mass-transfer limited.

Electrochemical reduction of carbon dioxide to ethylene

The following are electrode reactions:

Anode reaction: 2 H 2 O ( l ) → O2 ( g ) + 4 H +¿ ( aq)+ 4 e¿

+¿ ( aq ) +12e →C 2 H 4 ( aq ) +4 H 2 O ( l ) +0.07 V ¿
Cathode reaction: 2 CO2 ( g ) +12 H

Overall redox equation: 2 CO2 ( g ) +2 H 2 O ( aq ) →C 2 H 4 ( aq ) + 3O2 ( g )

The discovery and development of efficient technologies that enable the use of CO2 as a starting
material for chemical synthesis (at scale) is probably one of the biggest scientific challenges of
our time. But a key question is if the cure will not be worse than the disease?
➢ However, there are clear challenges for electrification, such as the overall high cost of
electricity, the large investment costs, from resent research, the economic feasibility of
the electrochemical reduction of CO2 to ethylene was assessed and it was demonstrated
that from a Capital expenditure and Operational expenditure point of view the
electrochemical production of ethylene from CO2 is not feasible under the current market
conditions.
➢ Even in the case that the renewable electricity prices would be zero, the feasibility is
hampered by the state-of-the-art catalyst performance (selectivity) and the cost of the
electrochemical reactor. Turning the installation on and off, if this would be even
practically possible, is not interesting because our study shows that because of the high
Capital expenditure, the payback time of the process would become unacceptably high.
➢ Furthermore, because of the high electricity requirement, this Carbon Capture and
Utilization process has a lower CO2 avoidance potential than the substitution of gray
electricity by green electricity. This means that today the available green electricity
would best be used to close coal and gas-based power plants instead of powering the
electrochemical conversion of CO2 to ethylene.
➢ Finally, the often poor selectivities and low conversions related to low reaction rates
(resulting in large reactor volumes needed for a world-scale plant), the technical and
economic feasibility of turning plants on and off safely on short notice, etc. This implies
that there is a lot of skepticism whether electrification of the chemical industry is actually
feasible (Van Geem et al., 2019; Gani et al., 2020) or whether it is another hype like the
numerous ones that have been presented in the last two decades (Banholzer,
2012; Banholzer and Jones, 2013).

Electrochemical reduction of carbon dioxide to formaldehyde

Challenges in electrochemical reduction of carbon dioxide to ethanol
The following are electrode reactions:

Anode reaction: 2 H 2 O ( l ) → O2 ( g ) + 4 H +¿ ( aq)+ 4 e¿

+¿ ( aq ) +12e →C 2 H 6 O ( aq ) +3 H 2 O (l )¿
Cathode reaction: 2 CO2 ( g ) +12 H

Overall redox equation: 2 CO2 ( g ) +3 H 2 O ( aq ) →C 2 H 6 O ( aq ) +3 O2 ( g ) +C 2 H 6 O ( aq )

The following are the challenges;
In recent years, strategies to design electrocatalysts for CO2 reduction to ethanol, a valuable
liquid fuel, have been increasingly reported. The mechanistic understanding providing insights
into steps of the reduction process has allowed for further development of highly efficient and
selective catalysts. Several significant breakthroughs have been made; however, the door toward
industrial-scale production of ethanol from CO2 is still wide open due to the following challenges
➢ Most electrocatalytic systems reported so far are still suffering from low energy
efficiency, inferior stability, and discouraging selectivity. For real-world CO2 electrolysis
application, further improvement in electrocatalytic activity is required, which should
fulfill the following demand: (1) small overpotential and high energy efficiency, (2)
satisfactory selectivity and faradic efficiency, and (3) good electrocatalytic stability
(>100 hr). To promote CO2 adsorption and activation, some useful strategies can be
adopted by surface modification, surface-structure tuning (surface defect, porosity,
crystallographic orientation, composition, strain, and curvature), and formation of
multiphase hybrid nanostructures.
➢ Scaling relations that exist between adsorption energies of different reaction
intermediates need to be circumvented, which can be realized possibly by selectively
stabilizing the inter mediates through some external stimuli.
➢ Other technical aspects, including acidic or alkaline working conditions, operating
parameters (such as pressure, electrolyte concentration, etc.), and electrolytic cells, must
be optimized. For the sake of desirable overall cell efficiency, high-performance
electrocatalysts to promote the anode OER (oxygen evolution reaction) are required as
well. Large-scale production of 2D nanosheets is the key to their practical use in CO 2
catalyst.
Electrochemical reduction of carbon dioxide to methane
The following are electrode reactions:
+¿ ( aq) + 4 e¿
Anode reaction: 2 H 2 O ( l ) → O2 ( g ) + 4 H
+¿ ( aq ) +8 e→ CH ( aq ) +2 H O (l)¿
Cathode reaction: CO 2 ( g ) +8 H 4 2

Overall redox equation: CO 2 ( g ) +2 H 2 O ( l ) → CH 4 ( aq ) +2O2 ( g )

The following are the challenges;
➢ Although major benefits to using CO 2 as a feedstock material for chemical production are
its potential to remove greenhouse gas from the atmosphere together with its presence on
Earth, Mars, and inhabited space stations (from metabolic production), there are
challenges to economic utilization (Zimmermann and Schomacker, 2017). A major
constraint that limits the deployment of CO2 utilization technologies is high production
 cost versus a typically lower-cost fossil-based incumbent on Earth (Spurgeon and Kumar,
2018).
➢ Among these CO2-derived compounds, CH4 has the lowest average market price as it is
the major component of natural gas, which has an October 2020 industrial price of $0.15
per kilogram in the United States (U.S. Energy Information Administration, 2020).
Technoeconomic assessment literature notes CO2-derived CH4 as one of the more
challenging products made from reduced CO2 to be competitive on a cost basis (Orella et
al., 2020). In CO2 methanation and power-to-gas technoeconomic assessments the cost is
typically over $4.00 per kilogram; thus, there is reliance on subsidy or low-cost hydrogen
with few examples of economic deployment (Peters et al., 2019; Becker et al., 2019).