Electrocatalytic reduction of CO2 into useful

chemicals-A Brief Review

1 2 3
M.B. Savitha , A. Jayarama and Richard Pinto

1
Chemistry Dept., Sahyadri College of Engineering and Management, Adyar, Mangalore, 575007

2
Physics Dept., Sahyadri College of Engineering and Management, Adyar, Mangalore, 575007

3
E & C Dept., Sahyadri College of Engineering and Management, Adyar, Mangalore, 575007

1
Email: [email protected]

Abstract 1 Introduction
Electro reduction of CO2 has become a subject of great
The electrocatalytic conversion of carbon dioxide (CO2 ) into
importance over the last few decades. This is fundamentally
useful chemicals has attracted many researchers worldwide
because CO2 is a notorious green house gas released both
for decades as it can enable a sustainable low temperature
by articial and natural processes. This review highlights
redox cycle for energy conversion and storage [1, 2]. While
current status and future directions in the electroreduction
CO2 is an essential substance for the growth of all plants
of CO2 into sustainable production of useful fuels. The
and for numerous industrial processes, it has now become a
current trends in understanding of CO2 reduction process
signicant greenhouse gas due to both natural and manmade
and the pathways through which various products are
processes [3-6]. In an ideal situation, CO2 consumed should
formed are discussed. Electro Catalysts play a very
be balanced with what is produced on Earth, so that the
important role in the CO2 reduction process to generate
− level of CO2 remains constant to maintain environmental
low-carbon fuels, including CO, HCOOH/HCOO , CH2 O,
stability. However, increased human industrial activities
H2 C2 O4 /HC2 O4− , C2 H4 , CH4− , CH3 OH, CH3 CH2 OH and
and consumption of fossil fuels has caused imbalance in
others. The electro-catalysts can be classied into several
CO2 concentration in the environment and has made
types, which include metals, metal oxides, metal alloys,
global warming an urgent issue. Hence, reduction of
metal complexes, polymers/organic molecules and others.
CO2 production and conversion of excess CO2 into useful
The vital characteristics of electro-catalysts which include
chemicals is critical, for environmental protection. Therefore,
product selectivity, activity, Faradaic eciency and catalytic
various governments all over the world have shown concern by
stability have been discussed in detail. The experimental
increasing their funding for research to address the CO2 issue.
evidence available so far indicates copper is the best catalyst
Hence, electrochemical reduction of CO2 into useful products
for electroreduction of CO2 into hydrocarbons. In particular,
and chemicals is urgently needed [7,8]. However, Carbon
recent developments showing high selectivity and faradaic
dioxide (CO2 ) produced by most hydrocarbon feedstock
eciency for generation of ethanol in oxygen derived copper
combustion processes is a thermodynamically stable product
nanoparticles as well as copper nanoparticles supported on
[9] and hence, reduction of CO2 is challenging.
carbon nano-spikes are extremely interesting. The review
also presents basic aspects of electrochemical cell for the
electroreduction of CO2 . Finally, the demonstration of During the last 30 years a great deal of research eort
feasibility of a two step CO2 conversion into liquid fuels and has been directed in the electrochemical reduction of CO2 .
the challenges in developing highly active and stable electro- Electrochemical conversion of CO2 into hydrocarbons was
catalysts for reduction of CO2 are discussed, indicating reported in 1985 by Hori et al. using cathode materials such
directions for future research and development in this very as Cd, In, Sn and Pb which predominantly gave formate
important area. and small amount of CO, CH4 and H2 . More importantly,
they reported the production of CH4 on pure copper as a
Keywords: CO2 conversion, CO2 reduction, Copper, cathode for the rst time [10]. In 1986, the same authors
Ethanol, electro-catalysis, Reaction mechanism. reported the production of CH4 and C2 H4 by electrochemical

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reduction of CO2 at Cu electrode in aqueous KHCO3 solution and the enediol(ate) would explain the observed selectivity
[11]. Later in 1988 J. J. Kim et al. reported that the onset of C2 pathway for the formation of C2 H4 [17]. New insights
potentials of ethene and methane were -1.5 to -1.6 V vs. were reported recently by K.P Kuhl et al. about the
saturated calomel electrode (SCE) and demonstrated that electrochemical conversion of CO2 on a Cu surface, which
CH4 is formed from CO at a rate 50 times lower than from was facilitated by an experimental method with excellent
CO2 with an onset potential of - 1.5 to - 1.6 V vs. saturated sensitivity for identifying and quantifying carbon dioxide
calomel electrode (SCE). The methane formation rate was electroreduction products. They studied Cu at dierent
higher if the surface was prepared by cleaning with HCl potentials and observed 16 dierent carbon dioxide reduction
rather than HNO3 , or oxidation in air [12]. In 1989, Y. products [18].
Hori et al. studied electrocatalytic conversion of CO2 in
aqueous inorganic electrolytes at Cu electrodes by means
J. H. Montoya et al. (2013) have presented a theoretical
of coulometric, chronopotentiometric, and voltammetric
study of C-C coupling in carbon dioxide electroreduction
measurements and reported the production of CO, C2 H4 ,
on the Cu (211) surface. They studied kinetic barriers to
CH4 , Ethanol and Prn OH at ambient temperatures. They
the formation of a carbon-carbon bond between adsorbates
reported that pH at the electrode is signicantly aected
derived from CO using DFT calculations. Their results
−
by the electrolyte, due to the formation of OH at the
demonstrate that kinetic barriers to carbon-carbon coupling
electrode [13]. Y. Tomita et al. (2000) have investigated
decrease substantially with the level of hydrogenation of
electrochemical reduction of CO2 at platinum electrode at
reacting adsorbates. They showed that the chemical potential
2
5 mA/cm current density in 0.1 M tetraethylammonium
of H2 can be changed through the applied potential in the
perchlorate acetonitrile-water mixtures. They reported that
electrochemical environment, which leads a variation of the
Pt can reduce CO2 primarily to oxalic acid in anhydrous
level of hydrogenation of the reactant chemicals, and thus
acetonitrile. They observed that the yield of formic acid
the activation barrier for C-C coupling [19]. W. Zhu et al.
increased and the oxalic acid formation dropped with the
(2013) have studied selective electrocatalytic conversion of
increase of water concentration. With further increase ◦
CO2 to CO on Au nanoparticles in 0.5 M KHCO3 at 25 C
of water concentration CO2 reduction was suppressed
[20]. In another experiment, D. Kim et al. (2014) have found
and hydrogen evolution prevailed. They found that Pt
that the factors related to the geometric eect, intermediate
electrode covered with CO behaves like the Pb electrode
binding, and the electronic eect, controls the activity of
[14]. Takahashi et al. (2002) have reported electrochemical
bimetallic Au-Cu nanoparticles. Great mass activities are
conversion of CO2 using two series of crystalline electrodes,
also shown by these nanoparticle monolayers, outperforming
Cu(S)-[n(111) × /(111)] and Cu(S)- [n(110) × /(100)]at 5
conventional CO2 reduction catalysts. They opined that the
−2
mA cm constant current density in 0.1M KHCO3 aqueous
insights gained through their study can serve as a basis for
solution. Using 99.999% copper metal, crystalline copper
designing better CO2 electrochemical conversion catalysts
was grown in a graphite crucible, and X-ray back reection
[21]. K Manthiram et al. (2014) have demonstrated that
method was used to determine the crystal structure. The
glassy carbon supported Cu nanoparticles (n-Cu/C) can
product distribution of CO2 reduction was found to vary
realize up to 4 times better methanation current densities as
substantially with the crystal orientation. Electroreduction
compared to electrodes of high-purity Cu foil. The n-Cu/C
of CO2 at the Cu(110) =Cu(S)-[2(111) × (111)] yields 20% of
electrocatalyst also shows an average Faradaic eciency
CH3 COOH and the yield of CH4 was only 6% at the Cu(110)
for 80% methanation during long electrolysis, which is the
electrode. The production of CH3 COOH and CH4 changed
highest Faradaic eciency reported at room-temperature
substantially with the crystal orientation [15].
methanation. They have found that the level of Cu catalyst
loading on the glassy carbon support has a signicant eect
on the surface morphology of Cu under catalytic conditions
A. A. Peterson et al. (2010) have given a theoretical
and the consequent Faradaic eciency for CH4 [22].
basis using density functional theory (DFT) calculations,
which explains unique ability of copper to convert CO2 into
useful fuels, which may lead to (photo-) electrochemical R. Kas et al. (2014) have reported the generation of
routes for the generation of fuels [16]. K. J. P. Schouten C2 H4 in CO2 electro-reduction over rough Cu electrodes and
et al. (2011) have proposed a novel mechanism for the explained that it is due to the presence of specic surface
electrochemical reduction of CO2 on Cu electrodes. They morphology. They demonstrated that similar electrode
show that CHOCOads is the key intermediate in the breaking coated with Cu nanoparticles can give either methane
of the C-O bond and, hence, in the production of CH4 . or ethylene, depending on the applied CO2 pressure and
It is also suggested that for the production of C2 H4 , the electrolyte concentration. Their pH calculation near the
rst step is the generation of a CO dimer, followed by the electrode surface shows that high local pH favors ethylene
generation of an enediolate or enediol, or the generation formation. Also, the conditions leading to the generation
of an oxametallacycle. In contrast to previously proposed of CH4 cause rapid reduction of hydrocarbon formation
FischerTropsch-like mechanisms, both the oxametallacycle rates, and electrode performance can be sustained for

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hours in conditions favoring ethylene production. This is the alloying of dierent metals in order to optimize the
study signicantly changes the mechanistic interpretation binding energies of reaction intermediates like COOHads .
of ethylene generation over rough Cu surfaces and shows Alloying might also be good for breaking scaling relations
that process conditions causing pH variations close to the between similarly adsorbed intermediates as they cause
surface of the electrode need to be considered [23]. Using intrinsic adsorption overpotentials. Additionally, product
DFT calculations D. H. Lim et al. (2014) have demonstrated selectivity can be inuenced by the pH of the electrolyte
that defective graphene-supported Cu nanoparticles can and the use of nonaqueous electrolytes instead of aqueous
change the electronic and structural properties of Cu for electrolytes. Therefore, optimal CO2 reduction systems
increasing electrochemical conversion of CO2 into useful fuels. require the conjunction of a catalyst with suitable adsorption
This paper provides better understanding of CO2 reduction properties and an electrolyte with benecial eects on the
mechanisms on both Cu and the Cu nanoparticle systems and catalytic activity and selectivity [29]. Au@Cu coreshell
explains factors responsible for enhanced CO2 conversion nanoparticles having well-dened surface structures have
[24]. H. Li et al. (2014) have identied the ensemble site been evaluated by J. Monz et al (2015), as catalysts for
for bond making and bond breaking on (100) surfaces as a the electrochemical conversion of CO2 in neutral medium
site consisting of two opposing bridge sites, i.e., a double- [30]. J. Rosen et al (2015) have reported computational
bridge ensemble site, based on extensive DFT calculations and experimental methods to investigate the electrocatalytic
of the mechanisms of dimethyl ether oxidation on platinum, reaction mechanism of carbon dioxide reduction on nano-
carbon monoxide reduction on copper, ammonia oxidation structured silver catalyst surfaces. They found that both
on platinum, and oxygen reduction on gold. The existence nanoparticle and nanoporous Ag catalysts show enhanced
of this site explains why these reactions all prefer the (100) ability to reduce the activation energy of the CO2 to
terrace and why steps and defects in the (100) surface lower COOHads reaction in comparison to bulk Ag catalysts [31].
the activity. Their work gives a fundamental understanding E. Bertheussen et al in 2016 have reported that acetaldehyde
for a particular type of structure sensitivity in heterogeneous is an intermediate in the electro-reduction of CO to C2 H5 OH
(electro)catalysis involving the making or breaking of bonds on oxide-derived Copper. They found that oxide-derived
between carbon, nitrogen and/or oxygen. Such unusual copper (OD-Cu) electrodes show excellent CO reduction
structure sensitivity is responsible for signicant deviations ability for hydrocarbons, forming acetate and ethanol with
in well-known scaling laws, which opens up the pathway for >50% Faradaic eciency at -0.3 V (vs.RHE). They identied
the design of superior heterogeneous catalysts [25]. Recently acetaldehyde as a smaller product but a key intermediate in
J. Wei et al. (2017) reported an ecient, highly stable the electro-reduction of CO to C2 H5 OH on OD-Cu electrodes
and multifunctional catalyst comprising of nanocrystalline using chromatography [32]. Stressing the carbon energy
HZSM-5 zeolite and Na-Fe3 O4 nanocatalyst. They reported cycle, CO2 + energy → methane → CO2 + energy, M.
that this catalyst can convert CO2 to gasoline-range (C5- Gattrell et al. (2006) [33] have emphasized that the synthesis
C11) hydrocarbons directly with CO2 conversion eciency of hydrocarbons from carbon dioxide is a complex multistep
of 22% and selectivity ∼ 78% under industrial relevant reaction process with mainly adsorbed CO intermediates.
conditions [26]. They have also stated that the reaction product distribution
is very sensitive to the surface crystal structure of Cu
electrode.
The particle size eect has been investigated by R.
Reske et al. (2014) for the catalytic electroconversion
Very recently, Y. Song et al. Oak Ridge National
of CO2 on 2-15 nm Cu nanoparticles and compared to
Laboratory (2016) reported an electrocatalyst which operates
bulk Cu. Nanometer-sized Cu nanoparticles exhibited a
in water at room temperature for the electro-conversion of
drastic enhancememnt in overall catalytic activity. Study
dissolved CO2 with better selectivity for ethanol. Their
of selectivity has shown that increased formation of CO
experiment shows that multiple reactive sites on nano-
and H2 accounts for the enhancement in the faradaic
structured surfaces in close proximity can give novel reaction
activity seen on the copper nanoparticles. The selectivity
mechanisms leading to high selectivity for a 12-electron
of hydrocarbons intially changed to a reduced plateau,
reaction. This indicates that the synergistic eect from
till it virtually disappears for nanoparticle sizes at and
interactions between copper and carbon nanospikes presents
below 2 nm [27]. R. Kortlever et al (2015) have shown
a novel strategy for developing highly selective electro-
that Pdx Pt(100x )/C nanoparticles have a reduced onset
catalysts. This path-breaking work by Y. Song et al. that
potential for the formation of CH2 O2 from CO2 , with
produces ethanol from CO2 with 63% conversion eciency
good selectivity. They showed the faradaic eciency for
could be an important pathway towards creating a low-
the generation of formic acid can be very high for the
carbon energy system [34-36].
Pd70 Pt30 /C nanoparticles depending on their composition
[28]. In another paper, they have discussed design strategies
for the development of selective and ecient catalysts for the However, many major issues still need to be
electro-catalytic conversion of CO2 . One of these strategies addressed before the elctrocatalytic conversion of CO2 into

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useful chemicals becomes cost-eective for technological
Table 1: Major Products of the Electrochemical Reduction
applications. The main problems faced today in
of CO2
electrocatalytic CO2 conversion are the high overpotentials 0
Sl.No. Product name and chemical formula k n m E
needed and the poor product selectivities and faradaic
1 carbon monoxide, CO 1 2 1 -0.10
eciencies. The poor product selectivities and high 2 formic acid, HCOOH 1 2 0 -0.20
overpotentials are mainly due to inappropriate adsorption 3 formaldehyde, HCHO 1 4 1 -0.07
energies of key reaction intermediates which are mediated 4 methanol, CH3 OH 1 6 1 0.02
by catalysts [37, 38, 16]. Further, the competing hydrogen 5 methane, CH4 1 8 2 0.17

evolution reaction (HER) which occurs in the same range of 6 ethanol, CH3 CH 2 OH 2 12 3 0.09
7 ethylene, C2 H4 2 12 4 0.08
potentials as that of CO2 conversion results in low faradaic
eciencies [39, 40]. Thus, catalysts need to be explored to
increase the eciency of electrocatalytic CO2 conversion In the past several years, many groups have studied the
and product selectivity while substantially lowering the mechanism of the CO2 conversion reactions [16, 17, 38, 45,
overpotentials. However, CO2 conversion into useful fuels 46]. It is understood that CO is an intermediate product
is very challenging primarily due to the multiple number of in the conversion of CO2 . DFT calculations show that
proton-coupled electron transfer steps [41]. In this paper, chemical dimerization step of CHO or similar adsorbates
a brief review of the electro-catalytic conversion of CO2 leads to ethylene formation [16, 46]. Schouten et al. [17,
into hydrocarbons based on work reported so far on the 45] experimentally demonstrated that the Cu(100) surface
eect of structure of catalyst, design of electrochemical cell, oers a specially active reaction pathway for the generation
electrolytic environment, temperature and other electro- of ethylene. The current major scientic challenges are
catalytic conditions. controlling the selectivity of the carbon dioxide conversion
reaction and reduction of over potential for the generation of
CH4 and C2 H4 . The geometry, roughness and morphology,
2 Reaction pathways of Cu polycrystalline and single crystal surfaces have shown a
strong eect on the product selectivity and catalytic activity
In order to understand the complex process of electrochemical
during carbon dioxide electroconverion [47-49]. Increased
CO2 reduction, it is important to dertermine, both
C2 H4 and CO generation was reported on roughened copper
theoretical [17, 42] and experimental reaction mechanisms
foils [48]. The changed selectivity was explained based
[16, 19, 37-38]. This will lead to more mechanistic insight,
on changes in the chemisorption characteristics of (100),
which will in turn, lead to better, tailor-made electro-
(111), and (211) surfaces of copper. Further, DFT studies
catalytic systems. In this section, we will discuss the current
showed that key intermediates like *CO and *CHO could
trends in understanding of CO2 reduction process and the
be stabilized on stepped surfaces having more negative
pathways through which various products are formed.
chemisorption energies [50].

The electrochemical conversion of CO2 can be viewed as a Ever since Hori made his landmark discovery in 1985 that
multiple proton-electron reaction leading to various products copper has the unique ability to electrochemically reduce CO2
and water as follows: to hydrocarbons such as CH4 and C2 H6 with good faradaic
eciencies in comparison to other catalysts [10] substantial

kCO2 + n(H + e) ↔ P + mH2 O (1) eort has been invested to understand the special reactivity
of copper for this reaction [33]. As mentioned earlier, CO is
Where P represents 'product' in aqueous media, k, n, an important intermediate in the production of hydrocarbons
and m are the coecients. Copper is currently the best- from the electro-conversion of CO2 on copper, [51] which is
known metal catalyst for electrochemical conversion of CO2 generally accepted in the literature. However, proposing a
[33,44] capable of electrochemical conversion of CO2 into conclusive mechanism for the conversion of CO2 on Cu is
more than 16 dierent products [18, 34] including CO, challenging, as seen by the recent nding of 16 products
CH4 , HCOOH, and C2 H4 or C2 H6 , ethanol, allyl alcohol, n- formed from CO2 [18]. Besides ethylene and methane, these
propanol, acetaldehyde, propionaldehyde, acetate, ethylene products include a wide mix of ketones, carboxylic acids,
glycol, methanol, glycolaldehyde, hydroxyacetone, acetone, aldehydes, and alcohols, out of which 12 are C2 or C3 species,
glyoxal [18, 33, 43] and others depending upon electrode showing the complexity of this reaction.
potential, pH of electrolyte, current density, catalyst surface
structure etc. Table 1 gives some of the important products of On the other hand, a carbene species (*CH2 ) on the
electrochemical conversion of CO2 with values of coecients surface, formed from *CO, was proposed to be a common
k, n and m provided in each reaction together with the intermediate for the production of methane and ethylene
standard equilibrium potentials. formation. Methane is then formed by double proton-electron
transfer to the carbene intermediate, while ethylene is formed

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Figure 1: One possible pathway for the electrochemical formation of methane from CO2 on Cu electrodes; values of k, n and
m are 1, 8 and 2 respectively.

by either dimerization of *CH2 species or addition of catalytic activity and stability is the greatest challenge in
CO in a Fischer-Tropsch-like step, which has also been CO2 electroreduction. During the past decades, most of the
suggested to be the pathway for the formation of alcohols eorts in CO2 electroreduction studies have been directed
[52]. In contrast with this "carbene" mechanism, Peterson on research and development eorts on electro-catalysts to
et al. have performed DFT calculations of the reduction solve the above challenges [56, 57]. This section specically
of CO2 to methane on Cu (211) surfaces, suggesting that focuses on electro-catalysts for electroreduction of CO2 into
the thermodynamically most favorable pathway, and at a useful hydrocarbons.
late stage of the mechanism, the second CO bond is broken
as shown in Figure 1 [16]. After the initial formation of
*CO, there is subsequent hydrogenation to *HCO, *H2 CO,
3.1 Electro-catalysts for CO2 electroconvers-
and *H3 CO, and this *HCO intermediate is reduced to
CH4 and *O, which is later reduced to H2 O. Ethylene is ion
produced by dimerization of H × CO species and subsequent
Transition metals, such as metal complexes are most
deoxygenation [19].
commonly investigated electro-catalysts for CO2 electro-
Although intensive experimental and theoretical studies
reduction, since their active d electrons and vacant orbits
have been carried out on electro-catalyst to understand the
support the bonding between CO2 and metal for the
mechanism of electro-chemical CO2 reduction, the detailed
formation of useful hydrocarbons and also facilitate the
mechanistic pathways are still uncertain. The important
release of the reduction products through catalyst surface.
problems are: slow kinetics of CO2 electroreduction, even
with high electrode reduction potentials applied on electro- 3.1.1 Pt group metals

catalysts; the low energy eciency of the process; and

Electroreduction of CO2 on Pt electrode was investigated
high energy consumption. The biggest challenge recognized
by Eggins and McNeill [58] in water, CH2 CN, propylene
by researchers in CO2 electro-catalytic reduction is the
carbonate, and dimethyl sulfoxide (DMSO) solutions.
insucient stability and poor performance of the electro-
Later, Brisard et al [59] studied the mechanism of CO2
catalysts. Hence, current research has to focus on promising
electroconversion catalyzed by polycrystalline Pt in acidic
metal catalyst such as copper with appropriate structure
media and found that the major product was CH3 OH. The
which will yield control of pathways and the production of
surface morphology of single-crystal Pt electrodes has been
useful hydrocarbons.
found to have a substantial inuence on catalytic activity for
CO2 reduction [60, 61]. Centi et al [62] converted CO2 to
hydrocarbons with long carbon-chain (>C5) at atmospheric
3 Role of electro catalysts
pressure and room temperature in a continuous ow cell using
The number and quantity of each species present in an carbon-supported nanoparticles of Pt (Pt/C) as the catalyst.
electrochemical cell strongly depend on the applied electrode Feng et al. [63] used a 3-D nano-structured porous electrode
potential, and type and selectivity of the electrocatalyst (nanoporous CuPt composites), for electroconversion of CO2
used. Most of the electro-catalysts used have insucient in ionic liquid BMIM. BF4 [63]. Recently, Pt/C-TiO2
selectivity, eciency and stability. Most of the catalysts and Pt-Pd/CTiO2 nanocomposite cathodes were used to
can survive for less than 100 hours [53-55]. This is much catalyze the electrochemical conversion of CO2 to CH4
lower than the requirements for commercialization. Hence, and isopropanol [64]. Electroreduction of CO2 on various
unsatisfactory catalysis, which includes selectivity, low conductive oxide mixtures(RuO2 ,TiO2 ,MOO2 ,Co3 O4 ,and

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Rh2 O3 ) exhibited, high current eciencies for CH4 formation Electrocatalysis of CO2 has also been tried with thin TiO2
when the electrode potential was xed close to the hydrogen lms or mixtures of TiO2 and other metal oxides normally
evolution equilibrium potential in a solution of 0.2 M Na2 SO2 deposited on Ti metal. In the preparation of a CO2 catalytic
(pH 4) saturated with CO2 [65]. Later, Bandi and Kuhne electrode, Monnier et al. [79, 80] prepared TiO2 , TiO2 Ru
[66] studied the electrocatalytic performance of mixed Ru/Ti (or RuO2 ), and TiO2 Pt thin lms by thermal evaporation
oxide electrodes; their results showed that increasing TiO2 on Ti rods. Bandi et al. (1990) [65] deposited RuO2 ,
content leads to increase in the overpotential for H2 evolution. TiO2 , MoO2 ,Co2 O4 , and Rh2 O3 on Ti foil and showed that
methanol and formic acid are major reduction products,
The electrocatalytic activity of Pd for CO2 reduction as identied by gas chromatography. Electro-catalytic
was initially investigated in a 1.0M NaHCO3 solution [67] synthesis of low-density polyethylene (PE) was realized
which resulted in HCOOH and CO as major products. from CO2 on a nano-structured TiO2 (ns-TiO2 ) lm in a
Further, small amounts of hydro-carbons evolved from a mixture of 1-Ethyl-3-Methylimidazolium Tetrauoroborate
Pd electrode catalyzed electrolysis process in CO2 -saturated (EMIM.BF4) and H2 O by controlled potential electrolysis
KHCO3 aqueous solution [68, 69]. It was found that CO at normal pressure and room temperature [81]. The ns-
yield increased signicantly with increase of CO2 pressure; TiO2 lm appeared to be signicantly ecient and selective
with electrode potential at 1.8 V vs. Ag/AgCl in 0.1M for the electro-chemical reduction of CO2 when EMIM.
KHCO2 , the yield increased from 5.3% at 1.0 atm to 57.9% BF4 was the solvent [81] as EMIM.BF2 maintained a high
at 50 atm [69]. It was reported that the evolution of H2 concentration of CO2 at the electrode surface. In another
can be reduced by H2 absorption on the Pd surface, and experiment, Qu et al. (2005) [82] loaded RuO2 onto TiO2
the absorbed H2 can modulate the electro-catalytic activity, nanotubes (NTs) or nanoparticles (NPs) to form RuO2 -
when it reacts with the adsorbed reaction intermediates [70]. TiO2 (NTs) or RuO2 -TiO2 nanoparticles, which were later
In another experiment, it was showed that hydrogenated coated onto a platinum electrode for the electro conversion
Cu-modied Pd electrodes have better catalytic activities, of CO2 . The potentiostatic electrolysis of CO2 on the RuO2 -
forming hydrocarbons such as HCOOH, CH2 , and CH2 OH TiO2 nanotubes coated platinum electrode showed 65.5%
[71, 72]. It has been reported that CO2 electroreduction on current eciency for selective formation of CH3 OH which is
Pd electrodes can take place at potentials more than the signicantly better than was realised on the RuO2 TiO2 (NP)
reversible hydrogen potential, indicating that adsorbed H2 coated Pt electrode.
−
atoms may take part in the electroreduction of HCO2 (CO2 )
−
to HCOO [73]. The CO2 electroreduction reaction on a Pd
3.1.4 Cobalt, Iron, and nickel
catalyst in a non-aqueous CH3 CN solution was studied by
Ohkawa et al [74] who compared the results with the results Electro-chemical reduction of CO2 on Ni, Co, and Fe

obtained in an aqueous solution and they showed that the electrodes, in aqueous solutions under normal conditions

concurrent desorption of H2 could lead to increased catalytic forms some hydrocarbons along with CO and H2 . These

activity for CO2 electroconversion. metals also have very signicant activities for CO2 and/or
CO hydrogenation in heterogeneous catalytic reactions. At
3.1.2 Molybdenum
30 atm, the electroconversion of CO2 at a current density of
−2
Electrodes of tungsten and Molybdenum do not show 120 mA cm the Fe electrodes formed HCOOH with ∼60%
signicant activity towards CO2 electro-reduction. Noda et Faradaic eciency [83]. Further, in the electro-conversion
al. (1996) [75] tested tungsten and Molybdenum electrodes in of CO2 at nickel electrodes in aqueous media, H2 and some
◦
KCl- saturated 0.1 M KHCO3 aqueous solution at 298 C at - hydrocarbons, such as CH4 , C2 H4 , and C2 H6 , were produced.
1.6 V vs. Ag/AgCl, and did not nd substantial catalytic The Faradaic eciency for CO2 reduction on Ni electrodes
activity for the electroconversion of CO2 . However, in could be enhanced by increasing the CO2 pressure, polarizing
another study D. P. Summers et al. (1986) [76] used Mo metal the electrode potential at a more negative potential, and
electrodes in the electrolysis of CO2 -saturated 0.2 M Na2 SO4 lowering the temperature [84]. In CO2 electroconversion
◦
aqueous solution (pH 4.2) at 20 C in -0.7 to -0.8 V potential catalyzed by Ni and Fe electrodes, CO adsorption on these
range vs. saturated calomel electrode (SCE) and found two metals was studied, and the results indicated that
greater than 50% Faradaic eciency, with major product the bonding between CO and the metal surface was very
being CH3 OH. Bandi et al [65] thermally decomposed a signicantly related to the catalytic activity [85].
mixed metal oxide consisting of 45% TiO2 , 30% MoO2 , and
3.1.5 Aluminum, gallium, indium, and thallium
25% RuO2 , on Ti foil to catalyze CO2 electroconversion to
CH4 , but signicant performance was not observed. Aluminum has been found to have low catalytic activity
for CO2 electroconversion [75, 86]. The reports show that
3.1.3 Titanium and Ruthenium
for electrochemical reduction of CO2 by aluminum electrode
Titanium has no substantial catalytic activity towards CO2 at -1.6 V vs. Ag/AgCl in 0.1 M KHCO3 aqueous solution
electroconversion [75]. However, TiO2 has been found to the Faradaic eciencies for generation of CH4 , C2 H4 , and
show some activity in electroreduction of CO2 [77, 78]. C2 H6 were as small as 0.58%, 0.04%, and 0.11%, respectively,

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with 99% for H2 evolution [75]. In another experiment, high to their high overpotentials for hydrogen evolution.
selectivity for CH3 OH formation was observed at very high
overpotentials using p-type Ga-containing semiconductors Reports show that electro-catalytic reduction of CO2 on
in a photo-electrochemical cell [87-89]. Further, Bocarsly Zn and Cd electrodes in 0.1M KHCO3 aqueous solution was
et al. (2008) [90] reported the highly selective conversion found to have good selectivity for the formation of HCOOH
of CO2 to CH3 OH at illuminated p-GaP electrodes, with and CO. On metallic Zn and Cd electrodes, the Faradaic
Faradaic eciency close to 100% for underpotentials larger eciencies of HCOOH were found to be 20% and 39%, while
than 300 mV at -0.52 V vs. SCE. CO2 electroreduction at In those of CO were 39.6% and 14.4%, respectively [75]. Shibata
electrode in aqueous media mainly forms formate [10, 91, 92], et al. [99] employed a Cd-loaded gas diusion electrode
but in nonaqueous solutions, the major product is CO [92]. to reduce CO2 and nitrite ions with various catalysts and
Kapusta and Hackermant [91] also reported ∼95% current observed that the maximum current eciency for urea
eciency in a 0.5 M HCOOH + 0.5 M HCOONa solution ((NH2 )CO) production was ∼55% at -1.0 V vs. SCE.
for CO2 conversion to formate. Further, the conversion of
CO2 to formate was studied by Narayanan et al [93] in
3.1.7 Tin and lead
an alkaline polymer electrolyte membrane cell with Indium
powder-coated porous carbon paper as cathode electrode. Tin electrodes were found to be very active towards CO2
For the cathode feed, three dierent aqueous solutions electroconversion forming HCOO- in aqueous electrolytes,
(CO2 -saturated deionized H2 O, 1 M NaHCO3 , and 1M but the major product was CO, with small quantity of
Na2 CO3 ) were used. The instantaneous Faradaic eciency glyoxalic acid, oxalic acid, and formic acid in nonaqueous
of formate production achieved in NaHCO3 solution was electrolytes [92, 94]. Some reports show that, Tin working
as high as 80% initially and it decreased to ∼ 10% over a electrode could catalyze CO2 electro-conversion in aqueous
period of 1.0 hour. Carbon mass transport was observed inorganic salt solutions to form formic acid with a high
to be the factor limiting Faradaic eciency. This mass current eciency ∼95% [10, 91]. However, organometallic
transport limitation can be reduced using high carbon dioxide complexes produced on the electrode surface during the
pressure or high bicarbonate concentration leading to stable reduction reaction process led to accelerated hydrogen
operation with high Faradaic eciency even at moderately evolution and consequent poor reaction eciency [91].
high current densities. On the other hand, Tallium electrodes
in aqueous electrolyte solution have been observed to increase
Increase of temperature caused a reduction in Faradaic
the production of HCOOH, while in nonaqueous solutions,
eciency for HCOOH formation and an increase for H2
C2 H2 O4 has been found to be the major product [92,94].
production [100]. Li and Oloman [101, 102] used a granulated
tin cathode with 99.9 wt% Sn and a CO2 feed gas in a new
reactor system and showed that the granulated tin cathode
3.1.6 Silver, gold, zinc and cadmium
gave higher performance than the Sn-Cu mesh cathode

When appropriate electrolytes are used both Au and Ag reported by them earlier, in terms of both current eciency

metals show signicant catalytic activity towards CO2 and stability [101, 103].

electroconversion [95]. The Faradaic eciencies for CO

0
production during CO2 electroreduction at Au(99.95%) and Using Sn and SnOx thin-lm catalyst prepared by
Ag(99.98%) metals in 0.1M KHCO3 aqueous solution at electrodepositing onto a Ti electrode, and CO2 - saturated
◦ aqueous NaHCO3 solution, Chen and Kanan [104] showed
25 C, at -1.6 V vs. Ag/AgCl saturated with KCl soution were
0
observed to be 81.5%, and 64.7% respectively [75]. Further, that Sn /SnOx catalyst showed upto eight-fold higher partial
it was reported [96] that when nanoporous Cu composites current density and four-fold higher Faradaic eciency for
(NPC) coated with silver were used in CO2 electroreduction CO2 conversion, more than that for tin metal coated with a
in BMIM.BF4 as electrolyte, dimethyl carbonate (DMC) native SnOx layer. They indicated that metal-metal oxide
could be electro-synthesized with a high yield of 80% composite electrodes are better catalysts for generation of

which was attributed to the large surface area with open hydrocarbons. CO2 electroreduction was carried out using

porosity and large eciency of silver coated NPC composite Pb electrode at -1.5 to -2.2 V vs. NHE in aqueous solutions of
electrodes. Sputter-deposited thin lm Au electrodes have ammonium salt, with a carbonate/bicarbonate buer which
been used for CO2 electroreduction [97]. The results showed was required to maintain 8.3 pH [105]. Pb catalyst in aqueous
that Argon pressure had an inuence on the geometrical electrolytes predominantly formed HCOOH; in non-aqueous
structure of surface area of Au surface, resulting in dierent electrolytes, C2 H2 O4 was the dominant product [92].

CO2 reduction potentials in both KCl and KHCO3 solutions.

A porous gold lm electrode prepared by vapor deposition Decreasing the temperature and increasing the CO2
was also used for the electroconersion of CO2 to CO in pressure increased Faradaic eciency on Pb electrode [106].
99.99% KHCO3 aqueous solution [98]. Zn and Cd electrodes With a high pressure of ∼50 atm and a high temperature
were considered as suitable electrodes for CO2 reduction due of ∼80◦ C, Pb granule electrodes with aqueous 0.2M K2 CO3

SAHYADRI International Journals of Research 24 |Vol 3| Issue 1|June 2017|

electrolyte solution, resulted in major reaction product formic the last few years in the development of new electro-
acid, with a high Faradaic eciency of 94% at -1.8 V vs. SCE catalysts based on copper which have greatly enhanced both
[107]. On the other hand, CO2 electroconversion carried out selectivity and Faradaic eciency for the generation of useful
at normal pressure and temperature, resulted in CO and CH4 hydrocarbons.
among other products [107].

The Copper electrodes so far developed are classied into

3.1.8 Alkaline metals and Other catalysts dierent types of electrodes: bulk Cu, in situ electrodeposited
Cu, Cu-electrodeposited GCE [10, 111, 112], Cu-coated GDE
Alkaline metals including alkaline earth metals cannot be
[113], Oxygen derived copper and Copper nanoparticles, and
utilized as catalysts for CO2 electro-conversion due to their
copper nanoparticles on N-doped Graphene [34]. Apart from
instability in electrochemical systems. Nevertheless, the salts
the low hydrocarbons such as CH4 , C2 H4 , CO, HCOOH,
of alkaline metals generally used for CO2 electro conversion,
alcohols (methanol, CH3 CH2 OH, and CH3 CH2 CH2 OH), and
as supporting electrolytes in electrochemical cells, exhibit
esters, some relatively high hydrocarbons-such as olens
dierent eects on reaction rate, product selectivity and
and parans having up to 6 carbon atoms-can also be
catalyst stability. Organic molecules can also function as
produced using copper electrodes [10, 11, 13, 75, 96, 114,
mediators and catalysts for CO2 electroconversion other than
115]. The Faradaic eciencies of these hydrocarbons are
the metals and metal complexes [108].
largely dependent on, type and concentration of electrolytes,
temperature, electrode potential, crystal surface, pH, and
Some conducting polymers have also been utilized for the
even the purity of the copper electrode.
heterogeneous electrocatalysis of CO2 electroconversion such
as poly-aniline (PAn); the maximum Faradaic eciencies
Crystalline Cu electrode surfaces are known to increase
were observed to be 12% for HCOOH and 78% for CH3 COOH
the electrocatalytic activity in CO2 electroreduction with
in CH3 OH solution [109]. In another experiment, a
the introduction of kinks and steps into atomically at
polypyrrole (PPy) electrode developed by Aydin et al. [109]
surfaces. Hori et al [15, 116, 117] were the rst to study the
was used in the electro-catalytic reduction of CO2 under high
electrochemical conversion of CO2 in 0.1 M KHCO3 aqueous
pressure in CH3 OH at an overpotential value of -0.4 V vs.
solution, at many types of Cu single-crystal electrodes. They
Ag/AgCl and the maximum Faradaic eciencies found at
observed that crystal orientation of copper electrode greatly
20 bar were 1.9, 40.5, and 62.2% for HCHO, HCOOH, and
alters the reaction selectivity. C2 H4 was the important
CH3 COOH, respectively.
product with electrodes based on (100) terrace surfaces. The
CH4 formation was increased at Cu(111) or by the addition of
3.2 Copper and Oxidized Copper (111) or (110) step atoms to the (100) basal plane. A Cu(S)-

Ever since Hori et al made their landmark discovery in 1985 [n(111) x (111)] electrode gave large quantity of reaction

that copper has the unique property as an electro-catalyst products having more than two carbon atoms, while a (110)

to reduce CO2 to useful fuels such as CH4 and C2 H4 with electrode derived from Cu(S)-[n(111) x (111)] specically

better faradaic eciencies in comparison to other catalysts produced high yields of CH3 CHO C2 H5 OH and CH3 COOH.

[10], substantial eort has been directed to understand the

special reactivity of Cu for this reaction [33]. CO was shown The catalytic activity of cuprous oxide (Cu2 O) derived
to be the key intermediate in the production of hydrocarbons copper nano-particles on hydrocarbon selectivity in
from the electro-conversion of CO2 on Cu [110], which is electrochemical CO2 reduction has been studied recently
now widely accepted in the literature. Copper is the most [118]. Cu2 O lms with dierent crystal orientations and
important electrode capable of catalyzing the production of variable thickness were electrodeposited by reduction of
substantial quantity of hydrocarbons at high reaction rates Cu (II) lactate on Cu plates. During electrochemical
over sustained periods of time; however, high over-potentials CO2 reduction by Cu2 O structures, it was found that the
are required during electro-reduction and a fairly broad mix selectivity of the process mainly depends on the thickness of
of major and minor hydrocarbons are formed [10]. Hence, parent Cu2 O, rather than on the initial orientation of Cu2 O
proposing a conclusive mechanism for the electro-conversion crystal [118]. Besides CO and H2 , selective production of
of CO2 on Cu is a challenging task [18]. Nevertheless, an C2 H4 was found with very high C2 H4 -to-CH4 ratios (∼8 to
insight into its unique ability to catalyze the formation of 12), while the thicker Cu2 O lms yielded a remarkably large
hydrocarbon would help in the synthesis of novel catalysts amount of C2 H6 . Further, analysis of long term Faradaic
that are active at a lower over-potential and with better eciency of hydrocarbons indicated no sign of deterioration
product control and simultaneously with good stablity. of the electrodes after 5 hours of continuous operation.
Authors also observed the conversion of the Cu2 O lms
While a detailed theoretical understanding of various in the presence of CO2 , generating a nanoparticulate copper
factors inuencing electrochemical reduction of CO2 is surface structure, before the formation of CO, hydrogen,
required, signicant progress has been achieved during and hydrocarbons using online mass spectroscopy and X-

SAHYADRI International Journals of Research 25 |Vol 3| Issue 1|June 2017|

ray diraction data. This process may lead to selective eciency up to 57% at modest potentials in alkaline H2 O
production of industrially useful product C2 H4 with the saturated with CO. The selectivity for oxygenates, with
optimization of surface area, size of the Cu nanoparticles, C2 H5 OH as the main product, shows the feasibility of a two-
and number density as well as local pH of the surface. step reduction of CO2 to hydrocarbons.

Christina et al. [119, 120] reported oxide derived In electrolytic cell for the reduction of CO2 , copper foil
nanocrystalline copper catalyst prepared by annealing copper catalyst forms a mix of reaction products in aqueous solutions
foil in air and electrochemically converting the resulting saturated with CO2 , which are dominated by (i) H2 at low
Cu2 O layers. They observed that the initial thickness of
−
overpotential, or (ii) CO and HCOO at high over-potential,
the Cu2 O layer strongly inuence the CO2 electro-conversion or (iii) multi-carbon oxygenates and other hydrocarbons at
activities of these electrodes. Thin Cu2 O lms grown by the very high potentials [18, 22, 34]. Theoretical studies
◦
annealing at 130 C resulted in catalysts whose activities have predicted that Cu nanoparticles supported on graphene
were similar to those of polycrystalline copper. On the other could increase electro-catalytic activity because of the strong
◦
hand, Cu2 O layers formed at 500 C with thickness ≥ 3µm copper-graphene interaction at defect sites [24] which in
resulted in catalysts that showed high surface roughness that turn could stabilize the intermediates from CO2 electro-
required 0.5 V less overpotential than polycrystalline copper conversion and improve the selectivity of hydrocarbons such
to convert CO2 at a higher rate than H2 O. The combination as CH4 and CH3 OH at lower overpotential. Studies have
of the above features gave CO2 reduction current densities also shown, that the catalyst surface gets strongly inuenced
2
>1/mA/cm at overpotentials <0.4 V which implied better by adsorbed CO during the CO2 electroconversion; also CO
activity. The authors also reported that the activity of acts as an intermediate in the generation of hydrocarbons [12,
the modied electrodes was highly stable, in comparison to 51]. Y. Song et al 2016) have reported [34] a nano-structured
polycrystalline copper electrode under identical conditions. catalyst for the electrochemical reduction of CO2 to C2 H5 OH
In another experiment, M. Le et al. (2011) [121] reported with high Faradaic eciency (63% at -1.2 V vs RHE) and
electro-reduction of CO2 to CH3 OH using several types of high selectivity (84%) that operates at ambient pressure
electro-catalysts including oxidized Cu electrodes. They and temperature. The catalyst they developed comprises
studied the yield pattern of an electrodeposited Cu2 O of copper nanoparticles as catalysts deposited on a highly
lm and explored relationships between reaction behavior textured lm of N-doped carbon nanospikes. With DFT
and surface chemistry of air-oxidized and anodized copper studies and electro-chemical analysis they have suggested a
catalyst. mechanism in which active sites on the copper nanoparticles
and the carbon nanospikes work together to control the
Faradaic eciencies (38%) and methanol yields (43 µ electrochemical conversion of CO dimer to CH3 CH2 OH. The
−2 −1 high selectivity for this 12-electron reaction indicates that
mol cm h ) obtained at Cu2 O cathodes were remarkably
higher than anodized or air-oxidized copper cathodes copper catalyst surfaces with nano-structures and multiple
suggesting Cu(I) species may play a major role in selectivity reactive sites in close proximity can yield novel reaction
to methanol. Authors also showed methanol yields are mechanisms. These are the best reported results so far in the
dynamic and the Cu oxides are reduced to copper in a electroreduction of CO2 into ethanol.
simultaneous process and indicated better stability of Cu(I)
species could allow continuous methanol production.
3.4 Catalyst stability and activity
degradation
3.3 Copper nanoparticles on Carbon
An understanding of the factors aecting the long-term
nanospikes
stability of electro-catalysts is of increasing importance for
Many catalysts [1, 120, 122-126] can convert CO2 to CO, the development of stable and ecient electro-catalysts as
but synthesis of liquid fuel requires that CO monoxide to electrode materials for electroreduction of CO2 with high
+
be further reduced with H2 O as a H source. Further, selectivity and Faradaic eciency. While activity of catalyst
though copper is the well known electrode with a signicant is assessed by considering the onset potential for conversion
CO electro-conversion activity, in bulk form its selectivity as well as the Faradaic eciency, catalyst durability is
and eciency for liquid fuel are very low for applications. evaluated as per the changes in the behavior of catalyst
Particularly, H2 O conversion to H2 is faster than CO with electrolysis time [102]. The production of poisonous
conversion on copper catalyst unless very high overpotentials intermediates and the deposition of inactive reactants on
are used; in such cases gaseous hydrocarbons will be the main surfaces of electrodes are reported to be the main causes
CO conversion products [52, 110]. Christina et al. (2014) for catalyst deactivation [112, 127-131]. Several possible
[120] also showed that, crystalline copper derived from Cu2 O factors for catalyst deactivation as summarized by Hori et
or 'oxide-derived copper' produces multi-carbonoxygenates al. [129] are: (a) heavy metal impurities present in chemical
such as acetate, ethanol, and n-propanol with Faraday reagents and subsequently added into the electrolyte solution;

SAHYADRI International Journals of Research 26 |Vol 3| Issue 1|June 2017|

(b) small quantity of organic molecules possibly contained in formation rate of CH4 for periods as long as 7 hours of
H2 O, and (c) intermediate species/products generated during electrolysis. Another technique used is pulse electrolysis
CO2 conversion and adsorbed as poisons on electrodes. In mode, which was observed to have a mitigating eect on
addition to these, catalyst stability can also be aected by cathode deactivation [146].
electrolysis condition and mode [119, 121, 132-134].
In other words, varying the electrolytic conditions led to
a signicant suppression of deposition of poisoning species
Further, Wu et al. [135] have observed that for pure Tin
on a copper catalyst, which mitigated the degradation of
catalyst, a drop in performance could be caused by many
the cathode. C. W. Li et al. [119] observed that Cu2 O
factors: (a) cathodic degradation of the catalyst electrode
◦
layers formed by annealing copper foil in air at 500 C
surface [136], (b) deposition of non-catalytic species on
catalyst surface (c) deposition of non-catalytic impurities
(thickness ≥ 3µ m) resulted in electrodes that showed large
surface roughness and needed 0.5V less overpotential than
from the electrolyte [135], and (d) anodic degradation at sites
polycrystalline copper to convert CO2 at a higher rate than
where gas bubbles are generated, which prevents cathodic
H2 O. Equally important, the activity of modied electrodes
polarization of the catalyst. For example, experiments
was stable over a period of several hours; on the other
conducted by Bujno et al. [137] showed that in diluted
hand, a polycrystalline copper electrode showed deactivation
solutions Ni(I) complex catalysts present at the surface of
within 60 minutes under similar conditions. In another
electrode were converted into a Ni(0) carbonyl deposit which
experiment, L. wang et al. [147] reported that (110) oriented
is catalytically inactive and hence, blocks the electrode
electrodeposited copper oxide lms were found stable in a
surface against further catalysis. In another experiment,
Benson and Kubiak [138] studied the deactivation pathway
very narrow pH range, ∼ 9.4 to ∼ 9.9.

of the Lehn catalyst and indicated that it is due to the

4 Electrochemical cell for electro-
production of thermodynamically stable and catalytically
inactive dimmers [139-141]. Pugh et al. (1987) [142] observed conversion of CO2
that the electro-catalytic activity of cis-[Ru(bpy)2(CO)H]+
The major limitations currently in CO2 electroconversion to
gradually decreased over a prolonged period. Active
generate useful fuels, are: (i) rapid degradation of catalyst
species/sites on catalyst surface are responsible for the
and (ii) slow transfer of CO2 to the surface of electro catalyst.
catalytic activity and hence are indispensable for electro-
Both of these limitations are somewhat related to the design
catalytic CO2 conversion [ 119, 140, 143, 144]. Hence,
of electrochemical cell. While it has been shown that
loss in activity of catalyst is linked with the loss of active
degradation of catalyst is primarily related to the catalyst
sites. One example is Ru-based complex catalysts slowly lose
material, the operating environment of electrolytic cell also
their carbonyl-containing complexes, due to the formation
plays a signicant role. Thus, while improving the stability
of inactive species such as [Ru(bpy)2(CO3 )] during CO2
of catalyst, it is also important to look into innovative reactor
reduction.
designs to optimize the operating conditions which will
result in better performance and long term stability. Some
In order to improve the activity and stability of the innovative designs for membrane-based electrochemical cells
catalyst, two major factors need to be considered: (1) the having gas diusion electrodes (GDEs) developed in recent
eect of type of catalyst, its composition and structure, years appear to be the better approaches for decreasing
and (2) operating conditions of the catalyst. An example internal resistance and improving the reactant mass transfer
of this phenomenon is Cu cathode deactivation after 3 process.
hours of electrolysis at constant potential, while the activity
of Cu catalyst remained stable for longer periods under In general, as mentioned above, the operating
superimposed potential method [145]. J. Lee et al. (2001) environment of the reactor is important for higher
[145] observed the adsorption of amorphous carbon during performance and stable operation of the electro-chemical
cathodic conversion of CO2 on Cu. After electrolysis for cell. For example, a decrease in the temperature and an
60 minutes at constant cathodic potential, the amorphous increase in the pressure lead to higher reaction rates due to
carbon cathode poisoning resulted in the reduction of faradaic an increased CO2 concentration in the electrolyte.
eciency for the production of hydrocarbons such as C2 H4
and CH4 . A change of the copper surface structure occurred While 0.5M KHCO3 is a widely used electrolyte, the use
with the production of Cu2 O, when the potential modulation of nonaqueous solutions improve CO2 solubility and decreases
method was used. This structural modication inhibited the hydrogen evolution reaction [43]. Reaction products
the amorphous graphite adsorption leading to the constant during CO2 reduction depend upon a variety of factors such

SAHYADRI International Journals of Research 27 |Vol 3| Issue 1|June 2017|

 Figure 2: Main reaction products of CO2 reduction on various catalysts.

as i) electrode/catalyst material, ii) Electrolyte including The Pt counter-electrode immersed in the electrolyte serves
pH and iii) applied potential. However, based on the main as an anode. A potentiostat and source meter are used to
reaction products they generate, electro catalysts can broadly provide a constant bias/current between the electrodes. The
be classied as shown in Figure 2 [13,148]. anode and cathode compartments are physically separated
by a proton-conducting membrane such as Naon
R
117.

In the rst group metallic copper is the only member The electrolyte solution typically used is aqueous solution

which shows exceptional activity and selectivity for CO2 0.5 M KHCO3 both in anode and cathode compartments

conversion to hydrocarbons and alcohols. Au, Ag and Zn, for CO2 reduction. A continuous ow of pure CO2 is

in the second group release CO as the major product. The introduced into the cell for saturating the electrolyte solution.

third group, consisting of In, Pb, Hg, Tl, Sn and Cd, produces This blocks interference from gas bubbles which strike the

formate as the major product; nally, hydrogen evolution is surface of electrode in the cathode compartment. The

mainly observed in Ni, Fe, Pt, Ga, and Ti cathodes. It is liquid products can be determined by sampling the liquid

interesting to note that CO is strongly adsorbed on electrodes in the cell and analyzing the composition of the solution by

of the fourth group; it is believed that the adsorbed CO blocks NMR Spectroscopy; The gaseous reduction products can be

further conversion of CO2 , giving rise in hydrogen evolution analyzed using Gas-chromatography.

[148].

The above discussion refers to the structurally simple

electrodes such as pure copper strip which is polished
with ne emery paper and subsequently electro-polished
in 85% phosphoric acid [13]. Electropolishing is generally
used to smoothen the surface and remove irregularities
after the mechanical polishing. Recent studies however,
have highlighted the inuence of the electrode surface
structure and the method of preparation. Single crystal
electrodes studies have shown that selectivity and activity in
electrocatalytic CO2 reduction depends on surface structure.
Further, it has been shown that the single crystal copper
electrodes with Cu(100) faces favor C2 H4 formation, while
those with Cu(111) faces show increased selectivity for CH4
[117]. Cu(110) faces show better yields for alcohols and non-
gaseous C2 and C3 products in comparison with others.

Figure 3 shows a typical electrochemical cell for CO2

electro-reduction. The electrochemical cell has a 3 electrode
conguration. The working electrode, the cathode, located
at a small distance from saturated Ag/AgCl electrode serving
as reference electrode to reduce the electrolyte resistance. A Figure 3: Schematic diagram of an electrolytic cell for electro-

Pt wire is used to make electrical contact with the cathode. catalytic tests of CO2 reduction in liquid phase.

SAHYADRI International Journals of Research 28 |Vol 3| Issue 1|June 2017|

5 Technological challenges in CO2 years in terms of product selectivity, catalytic activity, and
catalyst stability. However, technology has still not advanced
electrocatalytic reduction into to a stage to enable the use of electro-catalysts for practical

useful products applications of CO2 electro-reduction. Hence, breakthroughs

in electro-catalysis are essential.
Technological challenges in CO2 electrocatalytic reduction
into useful products are many, primarily due to: low product In the development of new catalysts, eort will have to be
selectivity, low catalyst activity, optimization of electrolyte directed towards synthesis of new catalyst materials with new
electrochemical cell design and insucient catalyst stability. structures to realise novel catalysts with better performance.
Hence, current technology is still far from adequate for Two important catalyst materials are: (i) nano-structured
practical applications of CO2 conversion to generate useful catalyst materials, and (ii) composite catalysts, which can be
fuels. Hence, development of highly selective, active, and synthesized by combining many dierent materials together.
stable electro-catalysts for the electro-conversion of CO2 is Optimized composite catalyst materials could have dierent
a major challenge. As described earlier in this review, for catalytic performance than their individual components
most of the catalysts developed so far, the overpotential for achieved with optimization of particle size, porosity, specic
CO2 electroconversion is rather too high, thereby suggesting catalyst surface area, and active sites. Optimized catalysts
that the activities of these catalysts are still not acceptable should prevent agglomeration of particles and facilitate
for large scale practical applications. Regarding low product proton and electron conduction, and protect active materials
selectivity, only some catalysts discussed above have resulted from mechanical and chemical degradation.
in better product selectivities and relatively stable yields
under continuous operation. For example, the use of
oxygen derived copper as well as nanoparticles on carbon 6 Summary
nano-spikes have given best selectivities to date for the
The catalyst materials with nano-structure, such as
generation of ethanol and methanol [32, 34, 121]. The single
nanoparticles, nanotubes/rods, nanoplates/sheet and others
biggest challenge currently in CO2 reduction is insucient
have unique properties, like high surface area and hence,
catalyst stability or durability. While there are reports
can provide easy diusion / transport pathways, leading
in the literature on stability tests upto 100 hours, there
to more ecient connectivity with electrolyte ions, faster
are no reports on long term tests. Among the problems
kinetics, and better active sites for the electrocatalytic
regarding stability of catalysts, generation of carbon lms and
process. Further, the nano-structured materials can also
poisonous species (reaction intermediates) on the electrode
be used as catalyst supports, such as copper nanoparticles
surface, which lead to poisoning and blocking of the active
on carbon nanospikes [34] for CO2 electroreduction. In the
sites on the surface of the catalyst is important. This leads to
present state of technology for CO2 electroconversion to
catalytic degradation as a reaction process. Among the other
produce hydrocarbon fuels, the main limitations are slow
challenges of electro-conversion of CO2 are optimization of
CO2 transfer to the cathode surface and rapid catalyst
electrodes and optimization of electrolytic cell.
degradation, both of which are partially related to reactor
design and the electrode. While catalyst degradation is
The nal challenge is the insucient fundamental primarily related to the cathode material, the operating
understanding of the CO2 reduction process, especially with environment of the cell also makes a signicant contribution.
regard to catalytic selectivity and activity. Hence, a great Hence, improving reactor design and the electrode, to
deal of work needs to be carried out not only via experiments optimize the operating conditions of the cell for enhancing
but also by theoretical modeling of activity and selectivity of catalyst performance and catalyst stability is important.
catalysts. Nevertheless, signicant progress has been made in certain
novel designs for gas diusion electrodes and electrolyte
This review gives an overview of development over several membrane-based electrochemical cells developed recently
decades as well as recent results in the catalysis of CO2 which help in improving the reactant mass transfer process
electroconversion. Various electro-catalysts are discussed and reducing internal resistance.
and classied into metals, its complexes, and conducting
polymers. The composition of electro-catalysts, conditions In summary, electroreduction of CO2 to generate
of reaction such as electrolyte, concentration, current or hydrocarbon fuels is a vital research and development area
Faradaic eciency, electrolysis potential, mechanisms of for reducing environmentally harmful CO2 . Despite the
CO2 electroconversion, and product selectivity are reviewed many advances, the process of CO2 electroreduction remains
in detail. In general, almost all the pure metals including still challenging mainly because of the poor solubility of
their composites which show some catalytic activity for CO2 CO2 in water at ambient pressure and temperature, the
electroconersion have been studied for their electro-catalytic high over potential required, the poisoning of electrodes by
activity. Some progress has been realized during the past few reaction intermediates and expensive separation techniques

SAHYADRI International Journals of Research 29 |Vol 3| Issue 1|June 2017|

of byproducts. It is strongly believed that with focused [12] J. J. Kim, D. P. Summers, K. W. Frese, and M.
and continued eorts on development of novel composite and Park, "Reduction of CO, and CO to methane on Cu foil
nano-structured electrode materials to solve the challenges electrodes", J. Electroanal. Chem. Interf. Electrochem.,
of low product selectivity, and catalytic activity, and also vol. 245, pp. 223-244, 1988.
catalytic stability, the technology of CO2 electroconversion
would become practical in the foreseeable future. [13] Y. Hori, A. Murata and R. Takahashi, "Formation of
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