A Review on Photocatalytic Reduction of Carbon Dioxide (CO2) to

Methane (CH4) using Copper as Electrocatalyst: Opportunities and

Challenges
ABSTRACT: Due to rapid accumulation of CO2 to the atmosphere mainly because of burning of
fossil fuels, different ways to tackle this problem have been introduced. Photocatalytic reduction
of CO2, which is just one those advantageous solutions, involves direct conversion of light to CO2
reduction product. In this review, the researcher highlighted the semiconductor-based
photocatalytic process based on the studies of Xie et al. (2016) and Fan et al. (2013) that
encompassed three main steps: (1) generation of electron-hole pairs after the absorption of
photons by the semiconductor; (2) separation and migration of photo-generated electrons and
holes to surfaces or the recombination of electron-hole pairs; and (3) oxidation of H2O (donor) by
holes to O2 and the reduction of H2O or CO2 (acceptor) by electrons to H2 or CO and organic
compounds. According to Xie et al. (2016), CH4 is one the most feasible hydrocarbons that can be
produced from the reduction of CO2. Fan et al. (2013) stated in their study that Cu is a widely
used electrocatalyst for CO2 photoreduction. Peterson and Nørskov (2012) supported this
information with 72.3% Faradaic yield for Cu in reducing CO2 to hydrocarbons/organics,
primarily CH4. Despite the advantages of CO2 photoreduction (Qiao et al., 2014), activating CO2
is a very difficult process and the products in the reduction of CO2 are considered complicated
ones (Xie et al., 2016). However, as of Peterson and Nørskov (2012), if CO2 can be
electrochemically reduced to hydrocarbons, then any of the renewable electricity sources can also
be used to create fuels.
Lechard R. Malapitan, 7:30 AM – 10:30 AM Friday, CEA420, BSEE 1-1, Department of Electrical
Engineering, College of Engineering, Polytechnic University of the Philippines.

Introduction
Fossil fuels are currently the major source of energy and are rapidly consumed to provide the
growing demands in energy of mankind. The combustion of fossil fuel generates carbon dioxide
as an inevitable by-product and may bring harmful effects in the environment (Mikkelsen et al.,
2010). Carbon dioxide (CO2) and its too much accumulation in the atmosphere, mainly because of
human-induced activities, has been considered as one the leading cause of climate change. This
carbon overload poses greatest risk of forming irreversible and adverse effects to environment as
well as to humankind (Union of Concerned Scientists, 2017). Due to the developing problems
concerning carbon emissions, various actions and solutions have been taken into motion to combat
and mitigate its detrimental impacts.
On the other hand, photocatalytic reduction with sunlight is an economical and promising
advanced approach to produce value-added fuels and chemicals products as well as for reducing
the excessive emissions of CO2 from the combustion of fossil fuels (Guan et al., 2018). CO2
photoreduction involves multi-electron processes which can lead to a large variety of products
ranging from carbon monoxide (CO) to higher hydrocarbons in the gas phase, and various
oxygenates in the liquid phase such as alcohols, aldehydes and carboxylic acids (Xu et al., 2013).
Despite the progressing direction of carbon dioxide utilization and its advantageous implications,
CO2 photoreduction is still held at early stage. However, the continuous effort put in widening this
field of research will possibly lead in further ways of making CO2 reduction more efficient,
advancing from its current standing.
For this particular review, the researcher focused on determining the efficiency of copper (Cu)
as an electrocatalyst in reducing carbon dioxide to methane (CH4) as well as some other products
based on already established studies regarding this subject. Moreover, this paper aimed at
providing some insights regarding the opportunities and fundamental challenges CO2 conversion
specifically with the use of photocatalytic reduction.
Methodology
In this section, the researcher tackled the methods used on recently established studies
regarding photocatalytic reduction of CO2 and presented some diagrams for further elaboration.
In the study of Xie et al. (2016) and Fan et al. (2013), the general photocatalytic process of
CO2 with H2O involves three main steps (Figure 1.1 and 1.2).

Figure 1.1. Basic mechanism of Figure 1.2. Schematic illustration of

photocatalytic reduction of CO2 with H2O on semiconductor-based photocatalytic process
a semiconductor photocatalyst (Xie et al., (Fan et al., 2013)
2016)

i. Generation of electron-hole pairs after the absorption of photons by the semiconductor

Electron–hole pairs are generated when a semiconductor photocatalyst is illuminated
by an appropriate light source with its energy equal or greater than the band-gap energy
(Eg) of the semiconductor.
The photon energy required for the photoexcitation depends on the bandgap of the
semiconductor. The semiconductor with a wider bandgap such as TiO2 (~3.2 eV) can only
utilize UV light, which accounts for ~4% of the total solar energy, while that with a
narrower bandgap such as CdS (~2.4 eV) can work under visible light (Fan et al., 2013).

ii. Separation and migration of photo-generated electrons and holes to surfaces or the
recombination of electron-hole pairs
Generated electrons and holes migrate to the surface of the semiconductor or a co-
catalyst in contact with the semiconductor (See Fig. 1.1iia). However, only a fraction of
carriers can reach the surface of the semiconductor or co-catalyst and the large fraction of
electron–hole pairs recombine together (See Fig. 1.1iib), with the energy being released in
the form of heat or photons.

iii. Oxidation of H2O (donor) by holes to O2 and the reduction of H2O or CO2 (acceptor) by
electrons to H2 or CO and organic compounds
The photogenerated electrons reduce CO2, which is adsorbed on catalyst surfaces, into
CO, HCOOH, CH3OH or CH4, whereas the holes oxidize H2O to O2.
According to Xie et al. (2016), the first and second steps are the same as those in the splitting
of H2O while the third step is peculiar to the reduction of CO2. The reduction of H2O could also
proceed in competition with that of CO2.
Results and Discussions
In this section, the researcher presented the data on different studies in which also answers
the objectives of this review.

A. Efficiency of Cu as Electrocatalyst in Photocatalytic Reduction of CO2

Photocatalytic CO2 reduction cuts out the electrolytic middleman in solar fuels synthesis.
Instead of relying on a photovoltaic panel for providing the electricity to drive electrolysis,
photocatalysis involves the direct conversion of light into a CO2 reduction product. Generally,
there are two options to promote the photocatalytic reaction. (1) A photocatalyst acts as both light
absorber and CO2 reduction catalyst, or (2) a light absorbing molecule (dye) or semiconductor is
used to sensitize a CO2 reduction electrocatalyst (Reisner and Windle, 2015).

Table 1. Redox potential of CO2 reduction with H2O on different reactions (Xie et al., 2016)

Reaction Redox Potential

E0 (V) vs. NHE (pH = 7)

CO2 + 2H+ + 2e- → HCOOH –0.61

CO2 + 2H+ + 2e- → CO + H2O –0.53

CO2 + 4H+ + 4e- → HCHO + H2O –0.48

CO2 + 6H+ + 6e- → CH3OH + H2O –0.38

CO2 + 8H+ + 8e- → CH4 + 2H2O –0.24

2H+ + 2e- → H2 –0.41

For the half-reaction such as reduction, the driving power is the negative redox potential and
the driving power is the positive redox potential for oxidation (Corrosionpedia, 2019). Based on
Table 1, formation of CH3OH and CH4 are more feasible because of their less negative redox
potential. Xie et al. (2016) stated in their study that the semiconductor, which is capable of
catalyzing the reduction of CO2 with H2O, should possess the conduction-band edge higher or
more negative than the redox potential for CO2 reduction.
Noble and coinage metals such as Pt, Rh, Pd, Ru, Cu, Ag and Au are widely used as
cocatalysts for photocatalytic H2 production and CO2 reduction (Fan et al., 2013). Pt and Cu
nanoparticles have been employed as bimetallic cocatalysts for photocatalytic conversion of CO2
with H2O over nitrogen-doped titania nanotube (NT) arrays. The cocatalysts significantly
accelerated the conversion of CO2 into CH4 and other hydrocarbons together with CO and H2 under
outdoor sunlight illumination (Mor et al., 2004).

Table 2. Faradaic Yields in CO2 Reduction (Peterson and Nørskov, 2012)

Faradaic Yield, %
Electrocatalyst Products

Hydrocarbons/organics (a) CO HCOOH H2

Cu 72.3 1.3 9.4 20.5

(a)
Predominantly CH4, but also includes C2H4, C2H5OH, C3H7OH, C2H6, C3H5OH, CH3CHO, and
C2H5CHO.
Table 2 shows the faradaic yield (in %), or the efficiency with which charge (electrons) is
transferred in a system facilitating electrochemical reaction (Bard and Faulkner, 2000), of Cu. It
is clearly shown in the table that the faradaic yield % in hydrocarbons/organics, primarily CH4, is
much higher (which is 72.3) compared to other three products (1.3 for CO, 9.4 for HCOOH and
20.5 for H2). In the study of Gattrell et al. (2006) it was shown that ethylene is also major product
in reducing CO2 using Cu as electrocatalyst with 50% faradaic efficiency.
Manthiram et al., (2014) suggested in their study the use of nanoscale copper electrocatalysts
in enhancing electrochemical methanation of CO2 for these are ideal for preparing gas diffusion
layers for membrane-electrode assemblies which can minimize polarization losses, maximizing
the energy efficiency of electrolyzers. In addition, these colloidally-prepared copper nanoparticles
have catalytic properties that rival much more expensive high-purity foils and single-crystal
electrodes.

B. Opportunities and Fundamental Challenges on CO2 Photoreduction

In recent years, CO2 conversion using electrochemical catalysis approaches has attracted
great attention for its several advantages: (1) the process is controllable by electrode potentials and
reaction temperature; (2) the supporting electrolytes can be fully recycled so that the overall
chemical consumptioncan be minimized to simply water or wastewater; (3) the electricity used to
drive the process can be obtained without generating any new CO2 sources include solar, wind,
hydroelectric, geothermal, tidal, and thermoelectric processes; and (4) the electrochemical reaction
systems are compact, modularon-demand, and easy for scale-up applications (Qiao et al., 2014).
Just as Xie et al. (2016) mentioned in their study, photocatalysis is one of the two highly
attractive routes for the reduction of CO2 with H2O to fuels and chemicals using solar energy. Even
though there have already appeared many articles and review papers, the progress in these areas
is largely behind that in the photocatalytic and photoelectrocatalytic splitting of H2O. Activation
of CO2 is a very difficult process and the products in the reduction of CO2 are complicated ones.
A variety of products (e.g., CO, HCOOH, HCHO, CH3OH, CH4, higher hydrocarbons and higher
alcohols) may be formed in the reduction of CO2 with H2O.
Even if CO2 photoconversion is still in the area of development, once amended, this can be a
promising progress and contribution not only to the scientific community but also to mankind's
growing demands in energy supply. According to Peterson and Nørskov (2012), unlike renewable
electricity, which can come from several sources (hydro, solar, wind, geothermal, and others),
renewable carbon-based fuels are currently only produced from biomass. The only other possibility
to produce such fuels is by chemically reducing carbon dioxide; if CO2 can be electrochemically
reduced to hydrocarbons, then any of the renewable electricity sources can also be used to create
fuels, simultaneously addressing storage issues for these often intermittent resources.

Summary
This section of the review paper presents the summary of all the findings drawn from different
articles and published studies regarding photocatalytic reduction of carbon dioxide, specifically to
methane using copper as electrocatalyst in order to meet the objectives of this paper: (1) determine
the efficiency of Cu as electrocatalyst in the conversion of CO2 to CH4 and (2) the current
opportunities and challenges for this process.
Based on the findings, the following conclusions have been drawn:

 Methane (CH4) is one of the most feasible product that can be produced from the reduction
of CO2 because of their less negative redox potential (Xie et al., 2016).
 Copper (Cu) is considered a great cocatalyst for photocatalytic reduction of CO2 to CH4
and other hydrocarbons yielding the highest Faradaic efficiency (72.3%) compared to other
 products such as CO, HCOOH and H2 (Peterson and Nørskov, 2012) and in the study of
Manthiram et al., (2014), the use of nanoscale copper electrocatalyst can greatly enhanced
the photoreduction of CO2 to CH4.
 Promising it may be, CO2 photocatalytic reduction is still a pioneer in the line of CO2
reduction. Activating CO2 is considered a difficult process and the products that can be
produced from this are regarded as complicated (e.g. CO, HCOOH, HCHO, CH3OH, CH4,
higher hydrocarbons and higher alcohols) (Xie et al., 2016). However, if CO2 can be
electrochemically reduced to hydrocarbons, then any of the renewable electricity sources
can also be used to create fuels, simultaneously addressing storage issues for these often
intermittent resources (Peterson and Nørskov, 2012).

Acknowledgement
The researcher would like to express his sincerest gratitude, first and foremost, to God
Almighty, in lighting up his mind and heart in the duration of the whole project. Next, for
unwavering dedication in teaching and inexhaustible guidance of Engr. Joie Florence Lacsa, his
instructor in Chemistry for Engineers, in order to complete his work; the most genuine appreciation
of the researcher is for her. Lastly, the researcher's gratefulness is dedicated to his family, friends
and other individuals who financially, spiritually and morally supported him all through.

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