Carbon Dioxide Electrocatalytic

Conversion on Electrodeposited Cubased Surfaces

R. Geronia II, M.F. Labata, K.L. Rosales
Department of Chemical Engineering, College of Engineering
University of the Philippines Diliman, Quezon City, Philippines

Abstract
Catalytic activity of copper-based surfaces in electrochemical carbon dioxide reduction was studied.
Electrodeposition of Cu-based surfaces on carbon substrate was carried out at different applied potentials in
lactic and sulfuric acid media using a three-electrode cell. Chronoamperometric runs were carried out for
each electrodeposit using a customized electrochemical set-up with CO 2-saturated KHCO3 as catholyte.
Control cathodic set-up was also done with N 2-purged electrolyte. Scanning electron microscopy images show
densely agglomerated cauliflower-like crystals that evolve to pyramid-like crystals for deposits in lactic acid,
while spherical and film-type structures are apparent for deposits in sulfuric acid. X-ray diffractograms also
confirm the dominance of Cu2O(111) and Cu(111) for catalysts synthesized in lactic acid and sulfuric acid;
however, at certain a certain potential, the presence of Cu 2O(111) is comparable with that of Cu(111) for
sulfuric acid-deposited catalyst. Results show that samples deposited at -0.7 V for both media attained the
highest current densities in the range of 13-14 mA/cm 2, signifying catalyst high activity at such potential.
Recommendations for further studies include determination of electroreduction products and assessing their
Faradaic efficiencies, and alloying of electrocatalysts with other metals active in CO 2 electroreduction.
Keywords: greenhouse gas; overpotential; product selectivity

product of COwill decrease reduction

overpotential, leading to a product rich in
hydrocarbons.

1. Introduction
2.
3.

4.
5.

Anthropogenic activity has significantly

contributed to global warming, which is a
phenomenon highly linked to presence of
greenhouse gases like CO2 in the
atmosphere. One method to sequester CO 2
from the atmosphere is by electrochemical
reduction, which is highly controllable,
easier to scale, and more compact than
other CO2 conversion technologies.

6.
7.

8.
9.

Chemical reduction of CO2 works through

the use of a reducing agent to lower the
oxidation state of its carbon atom. The
process may or may not involve hydrogen
addition to the carbon. According to Willner
& Willner (1991), products of singleelectron reduction from CO2 are less stable
from a thermodynamic point of view. For
this reason, processes that utilize multielectron reduction, which produces more
stable products, have been developed; for
example, in the high-pressure formation of
formic acid from CO2 using a rhodium
catalyst. However, the amount of energy
needed to transfer multiple electrons (i.e.,
potential
difference)
prohibits
its
widespread use, necessitating the use of
catalysts
to
increase
selectivity
by
decreasing reduction overpotential. In fact,
density functional theory (DFT) studies by
Peterson and colleagues suggest that the
efficient adsorption of CHOa protonation

To date, homogeneous catalysts usually

involve metal complexes and electrolytes.
Still, competing reactions in aqueous
electrolytes such as hydrogen formation
and CO2 hydration decreases production
efficiency, warranting further studies on
improving the reduction process.
Among catalysts studied in the past
decades, only copper has exceptional
selectivity and activity to convert the gas
to hydrocarbons at ambient conditions.
High overpotentials, low current densities,
and deactivation however plague Cu and
thus, numerous literature recommend its
modification with Cu oxides. By growing
oxides on top of Cu, a highly-structured
surface is obtained.

10.
11. Some studies suggest that Cu2O is rapidly
reduced
then
remains
as
Cu.
Cu
nanoparticles are therefore formed in situ.
Defects in the surface could be the cause
why these nanoparticles are known to have
good selectivity for ethylene. Moreover,
tuning a particular Cu facet can cause
preference
towards
a
particular
hydrocarbon during reaction. On the other
hand, there have been studies as well

wherein
catalyst
morphology
product distribution.

affects

32. A customized electrochemical set-up,

shown above, was used for both lactic acidand sulfuric acid-deposited catalysts. The
anodic and cathodic compartments, which
contain the Pt wire and the carbon paper,
respectively, were separated by a Nafion
115
membrane.
Similar
to
the
electrodeposition set-up, platinum wire and
Ag/AgCl served as the counter and
reference electrodes.
33.
34. Aqueous 0.1 M KHCO3 (Sigma Aldrich,
99.7%) prepared from deionized water and
saturated with CO2 , with saturation point
determined from a change in pH from basic
to pH 7, was used as the electrolyte. The
reactor was then subjected to cyclic
voltammetry (CV) scans in the range of -1.0
V to 0.0 V versus Ag/AgCl, at a scan rate of
10 mV/s. Control cathodic experiments
were also performed with purged N2.
35.
36. After the CV scans, reduction via
chronoamperometry was initiated. At the
tenth minute, CO2 at a flowrate of 1 L/min
was reintroduced to the 80 mL 0.1 M KHCO3
catholyte for 5 minutes to ensure sufficient
CO2
supply.
Reduction
at
ambient
conditions was performed for 30 minutes at
-1.9 V versus Ag/AgCl for all samples.
37.
38.

12.
13. In addition to morphological assessment
using scanning electron microscopy and Xray diffraction, by observing current
densities during CO2 reduction, activity of
Cu as a catalyst is assessed. This would
then help in identifying the deposition
conditions optimal for the reduction of CO2.
14.
15. With this, the research aims to observe the
activity of copper-based electrodeposits on
the reduction of carbon dioxide. Catalyst
activity is quantified through current
density, which is identified using cyclic
voltammetry during CO2 reduction.
16.
17.

18.

Materials and Methods

19.
20. 2.1 Synthesis of Electrocatalysts
21.
22. In this study, two Cu-based surfaces will be
synthesized
using
different
electrodeposition media: lactic and sulfuric
acid. Used in deposition is a customized
three-electrode
set-up
comprised
of
Ag/AgCl in 3 M NaCl solution as the
reference electrode, 4 cm2 Sigracet 10BC
as the working electrode, and a Pt wire as
the counter electrode. Autolab PGSTAT302N
was used for potentiostatic control.
23.
24. For the lactic acid medium, a solution
containing 0.4 M CuSO4 (CuSO45H2O, Loba
Chemie 99%) and 3 M lactic acid (Loba
Chemie, 88%) was prepared. The set-up
was maintained at 60C and pH 9.0 using 4
M NaOH (NaOH pellets, Sigma Aldrich
>97%) during deposition. On the other
hand, the plating bath for the sulfuric acid
medium consisted of 0.4 M CuSO4
(CuSO45H2O, Loba Chemie 99%) and 1.0 M
H2SO4 (analytical grade), which was
maintained at room temperature. For both
media, linear sweep voltammetry (LSV)
was carried out at a scan rate of 10 mV/s to
determine onset potentials for deposition.
Through inspection, potentials of -0.4 V,
-0.5 V, -0.6 V, and -0.7 V were identified as
the potentials in which to perform
deposition. Deposition in the lactic acid
medium was performed for 20 minutes
while that in the sulfuric acid medium, 1
minute.
25.
26. 2.2 Characterization
27.
28. Scanning electron microscopy (SEM) at
500x, 1000x, and 10000x magnification,
and X-ray diffraction (XRD) analyses were
conducted to identify the catalysts surface
morphology and bulk-phase structure,
respectively.
29.
30. 2.3 Electrochemical Measurements
31.

39.

Results and Discussion

40.
41. Linear sweep voltammetry with a scan rate
of 10 mV/s was performed in both lactic
and sulfuric acid media. As seen from the
curves in Figure 5, the sweeps for the two
set-ups start at 0.2 V vs Ag/AgCl, where the
observed current densities were around
zero. Then, an increased drop in the
cathodic current densities were seen for
both curves at -0.2 V and -0.1 V for lactic
acid and sulfuric acid, respectively.
42.
43. Through the LSV curves, four deposition
potentials were selected for each of the two
media; these were from -0.4 V to -0.7 V at
-0.1 V intervals. The chosen applied
potentials are in the potential window for
reduction, where a sudden increase in the
current densities was observed. This could
then imply the possible reduction of Cu2+ to
Cu2O or Cu and the deposition of the
reduction products on the carbon paper
substrate.
Deposition
at
extremely
negative potentials was avoided due to
hydrogen evolution reaction (HER) being
predominant at higher cathodic current
densities. HER is usually exhibited by low
coordination numbers of majority of the
surface population of Cu atoms. The
uncoordinated Cu atoms are expected to
be more strongly chemisorbed to atomic H
as compared with planar Cu atoms, thus
leading to enhancement of HER and
suppression of CO2 reduction.[32] In the

same study, HER is attributed

increase in Cu2O film thickness.

to

an

from open-circuit voltage to -1.0 V. All

catalysts were tested at N2-saturated and
CO2-saturated electrolyte, with the former
as the control.

44.
45. Surface morphologies of the synthesized
Cu-based catalyst were analyzed using
scanning
electron
microscopy.
The
electrocatalysts were subjected to three
different magnifications: 500x, 1000x and
10,000x as shown in Figure 6. Examination
of the SEM images show that the surface
morphology of the catalysts changed with
deposition potential for both acid media. At
10,000x magnification, the morphology of
the electrodeposited Cu-based surfaces in
lactic acid medium evolved from densely
agglomerated cauliflower-like structure at
-0.4 V to pyramid-like crystals from -0.5 V
to -0.7 V.
46.
47. For the sulfuric acid medium, spherical and
film-type structures were formed. At -0.4 V,
spherical structure dominates the surface
while at -0.5 V, a film-type structure begins
to develop and the spherical structures
were reduced in particle size. The spherical
structure then begins to re-appear at -0.6 V
with smaller particle size than that at -0.4
V. Finally, a film-type structure becomes
more apparent at -0.7 V, with tiny crystals
embedded on the surface. The spherical
structures were highly porous in nature due
to hydrogen-assisted deposition occurring
in highly acidic conditions. Similar to the
hydrogen templating method, hydrogen
gas is evolved during deposition. The gas
then prevents the contact of the electrolyte
with the carbon paper substrate, impeding
the electrodeposition of copper in the
electrolyte. Afterwards, a thin film of
electrolyte surrounded by the gas comes in
contact with the electrode and allows the
electrodeposition of copper[66].
48.
49. The fabricated catalysts were further
characterized using X-ray diffraction to
confirm their bulk chemical composition
and structure. The XRD pattern shown in
Figure 7 shows that the catalyst surface
deposited in the lactic acid medium is
predominantly Cu2O(111), while Cu(111) is
the major facet in the surface of the
catalyst deposited in the sulfuric acid
medium except at -0.7 V where a
comparable amount of Cu2O(111) was also
formed. Catalysts synthesized using lactic
acid yielded similar peaks throughout the
four deposition potentials while for sulfuric
acid media, the peaks for catalyst made at
-0.7 V showed some observable deviations
to that of the rest of the potentials. This
could be due to the condition of very acidic
environment and extremely negative
potential experienced by the catalyst.
50.
51. Electroactivity of the catalysts towards CO2
electroreduction were determined by cyclic
voltammetry
and
chronoamperometry.
Cyclic voltammetry was performed at a
scan rate of 10 mV/s and a potential range

52.
53. Cyclic voltammogram curves for N2- and
CO2-saturated electrocatalysts are shown in
Figure 8. The difference of the curves from
the two saturated electrolytes confirms CO 2
electroreduction. For catalysts in lactic acid
medium, Cu electrodeposits at -0.6 V and
-0.7 V were more electroactive as they
yield higher cathodic current densities. The
opposite was observed for electrodeposits
in sulfuric acid medium, where those
deposited at -0.4 V and -0.5 V were more
electroactive.
Nonetheless,
catalysts
synthesized in sulfuric acid medium have,
in general, higher cathodic current
densities than those synthesized in lactic
acid medium. This can be attributed to the
catalyst having a more porous structure
than that synthesized in lactic acid, and
hence having more active sties for CO 2
reduction to occur.
54.
55. Chronoamperometry was also employed at
a fixed potential of -1.9 V vs Ag/AgCl for 30
minutes. This potential for electrolysis was
selected
according
to
a
similar
experiment[65]; -1.9 V is an intermediate
potential appropriate for exploring the
influence
of
crystallography
and
composition of the electrodes. Carbon
monoxide is essentially formed in the gas
phase at low overvoltage, while at very
high overvoltage CH4 is highly favored and
the concentration of CO
decreases
significantly using Cu as catalysts.
56.
57. In the experiment, the KHCO3 electrolyte
was first saturated with CO2 at a flowrate of
1 L/min until the solution reached pH 7. The
pH was controlled for two reasons: one, a
high pH promotes the formation of
hydrogen carbonate and carbonate through
the conversion of dissolved CO2 and two, a
low pH limits the contribution of hydrogen
evolution reaction[65].
58.
59. After 10 minutes of electrolysis, a marked
decrease in the cathodic current densities
in both media was seen as CO2 was
reintroduced into the system. Bubbling of
CO2 was done for five minutes to ensure its
presence
during
the
CO2
reduction
experiment, and that the amount of CO 2 in
the system is sufficient to form reduction
products. However, CO2 bubbles might
have blocked the surface of the catalysts,
leading to a disturbance of the steady-state
condition of the reaction and eventually
causing a sudden decrease in the cathodic
current densities. Regardless, the current
density eventually reached a steady state
after the flow of CO 2 was stopped, although
now at a lower steady-state value. For the
30-minute electrolysis, catalysts deposited
at -0.7 V for lactic acid and sulfuric acid

had the largest cathodic current densities

at around -13 and -14 mA/cm2, respectively.

four deposition potentials (-0.4 V to -0.7 V,

at -0.1 V intervals) were selected; the
points could signify the potential window
for the reduction of Cu2+ in the electrolyte.
Characterization of catalysts in terms of
morphology and bulk phase composition
were done using scanning electron
microscopy
and
X-ray
diffraction,
respectively. For lactic acid-based catalysts,
the morphology evolved from densely
agglomerated cauliflower-like structures to
pyramid-like crystals with Cu2O(111) being
dominant on the surface. On the other
hand, catalysts made under sulfuric acid
had structures that were either porous and
spherical
or
film-type
with
crystalembedded surfaces depending on the
potential; dominant facet is Cu(111), but a
comparable amount of Cu2O(111) was
formed at -0.7 V. The highly porous nature
of sulfuric acid-based catalysts can be
attributed
to
a
hydrogen-assisted
deposition considering that the plating
solution was highly acidic.

60.
61. Although product identification was not
performed for the catalysts synthesized
under two media, insights from literature
could help probe the possible products
formed from the electrolysis experiment. In
a study focusing on the catalytic
performance of Cu and Cu2O[67, it was found
out that after two hours of electrolysis, Cu
is more selective towards CH4 formation,
although with the Faradaic efficiency
decreasing from 52% to 25%. On the other
hand, Cu2O is found out to be more stable
and selective towards ethylene, having a
consistent Faradaic efficiency of 22%. The
result of the said study is displayed in
Figure 10.
62.
63. Another work on Cu(111) surfaces showed
similar performance with respect to the
production of CH4 after 30 minutes of CO 2
electroreduction. In the work, it was
inferred that CO could not be adsorbed at
Cu(111) at high enough coverage and also,
that HER is not affected. In contrast, a shift
of the HER to a more negative potential is
seen in other Cu facets such as Cu(110)
and Cu(100) due to high CO coverage.
Mechanism for the formation of C1 product
was discussed, with adsorbed CHO (CHO ads)
acting as the primary intermediate.
Formation
of
CHOads
requires
the
simultaneous presence of Hads and COads,
and there is a higher probability of finding
an adjacently adsorbed CO and H on a
high-density surface like Cu(111). Thus,
formation of CH4 is highly favored when
adsorption of hydrogen is promoted.
64.
65. On the other hand, the catalytic activity of
Cu2O catalyst towards CO2 reduction has
also been examined in some papers [32,61],
confirming that Cu2O films are not stable
during
the
reduction
process,
only
eventually reducing to Cu0. Spherical
structures of Cu2O after the reduction
process are now composed of nanometer
scale Cu domains. Similar result was also
found in this experiment where a change in
the appearance of the electrodeposit at
lactic acid-medium could have reduced in
situ to metallic Cu as evidenced in Figure
11. Although many other Cu2O facets could
be formed, its initial orientation does not
affect
catalyst
selectivity
towards
ethylene[61].
66.

70.
71. The synthesized catalysts were tested in a
customized electrochemical set-up using
0.1 M KHCO3 saturated with CO2 at pH 7.
Cathodic current density was monitored in
both
cyclic
voltammetry
and
chronamperometry
tests.
In
cylcic
voltammetry, sulfuric acid-based catalysts
generated larger cathodic current densities
compared to lactic acid-based catalysts,
which could be explained by the highly
porous morphology of sulfuric acid-based
catalysts. For the 30-minute potentiostatic
chronoamperometry, catalyst fabricated at
-0.7 V for the two acid media exhibited the
highest current densities at around -13 and
-14 mA/cm2.
72.
73. For further studies, it is recommended to
perform a long-term electrolysis for the -0.7
V catalysts synthesized in both lactic acid
and sulfuric acid media to ascertain its
stability.
Characterization
after
CO2
reduction must also be done to examine
changes in morphology and bulk phase
composition. Formation of methane and
ethylene products should be confirmed,
comparing results from those published in
literatures.
Corresponding
Faradaic
efficiencies, which is related to the
selectivity of the catalyst, should also be
evaluated.
Lastly, alloying with other
metals active in CO2 electroreduction (such
as gold) could be explored and be tested if
it improves the performance of Cu-based
electrocatalysts.
74.
75.

67. Conclusion and

Recommendations
68.
69. In
this
work,
eight
Cu-based
electrocatalysts were synthesized from two
different acid media: lactic acid and sulfuric
acid. Through an inspection of cathodic
current densities in the linear sweep
voltammetry curves of the two acid media,

76.

Works Cited

77.
78.
Willner and B. Willner (eds.). (1991).
Artificial Photosynthetic Model Systems Using LightInduced Electron Transfer Reactions in Catalytic
and Biocatalytic Assemblies in: Photoinduced

Electron Transfer III, J. Mattay. Berlin, Germany:

Springer-Verlag.

79.

80.

81.