Research Article

pubs.acs.org/acscatalysis

Controlling the Product Syngas H2:CO Ratio through Pulsed-Bias

Electrochemical Reduction of CO2 on Copper
Bijandra Kumar, Joseph P. Brian, Veerendra Atla, Sudesh Kumari, Kari A. Bertram, Robert T. White,
and Joshua M. Spurgeon*
Conn Center for Renewable Energy Research, University of Louisville, Louisville, Kentucky 40292, United States
*
S Supporting Information

ABSTRACT: The electrochemical reduction of CO2 is a

promising method for sustainable, carbon-neutral chemical syn-
thesis as well as the storage of intermittent renewable energy in the
form of energy-dense fuels compatible with existing infrastructure.
In this work, we investigated a pulsed-bias technique for CO2
reduction on Cu, which led to a major shift in the product
selectivity relative to potentiostatic electrolysis conditions. With
applied voltage pulses in the millisecond time regime, syngas (CO
+ H2) became the only product and had a pulse-time-dependent
H2:CO molar ratio, ranging from ∼32:1 to 9:16 for pulse times
between 10 and 80 ms, respectively, at the same applied working
potential. X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) data suggested that in situ oxidation and
reduction of the Cu partially caused the preference for CO formation over other carbon products on polycrystalline Cu.
Significant nonfaradaic current arising from electrical double layer charging and discharging was also suspected to contribute to
the desorption of key reaction intermediates and further promote CO. The results provide an electronic technique for the
electrochemical production of a controllable syngas feedstock for utilization in numerous industrial applications (e.g., Fischer−
Tropsch process and hydroformylation of alkenes to aldehydes).
KEYWORDS: copper, catalyst, CO2 reduction, syngas, selectivity, electrochemistry

1. INTRODUCTION oatomic carbon nanomaterials.10 Among these catalysts,

As societal energy demand continues to increase, the burning of
fossil fuels to provide a majority of this energy will emit
greenhouse gas CO2 at a rate that will put progressively greater
strain on the global environment.1 Among various emerging
CO2 mitigation technologies2 (e.g., sequestration,3 chemical
conversion,4 and electrochemical reduction), the electro-
chemical CO2 reduction reaction (CO2RR) has advantages as
a means to sustainably utilize this waste stream to produce
valuable chemicals and fuels.5 For instance, electrochemical
conversion is directly controllable by adjustment of the applied
electrode potential, and an electrochemical system can operate
near room temperature, have a relatively small footprint,
require minimal chemical intake, and be easily scaled up. With
the electricity supplied by intermittent renewable sources (i.e.,
solar and wind), CO2 reduction is also an ideal method to store
energy as chemical bonds in the form of energy-dense
molecules (e.g., syngas, ethanol, methane, etc.) for clean
power utilities and transportation fuels.6 Because of the stability
of the CO2 molecule, the cathodic reduction overpotential is
significant, and thus highly active and selective electrocatalysts
are necessary to efficiently promote CO2RR over hydrogen
evolution.
Numerous heterogeneous catalysts have been employed for
CO2 electrochemical reduction, including transition metals7
and transition metal oxides,8 metal complexes,9 and heter-
relatively inexpensive and earth abundant copper (Cu) metal
has the unusual property of producing hydrocarbons from
CO2RR, and has therefore been widely studied for this
reaction.11 However, unlike Ag7b,12 and Au,7c,d,f Cu has
relatively poor CO2 reduction product selectivity due to the
multiple competing reaction pathways it can promote as well as
a sensitivity to crystal orientation leading to variability from the
heterogeneity of active sites present on the polycrystalline
surface.7e,13 As many as 16 products (e.g., methane, ethylene,
formic acid, carbon monoxide, etc.) have been identified from
the electrochemical reduction of CO2 on a polycrystalline Cu
film.7e Consequently, numerous efforts have been pursued to
enhance the selectivity of polycrystalline Cu by fine-tuning the
structure,14 size,15 morphology,16 and composition,13a but
controlling the CO2RR reaction pathway remains a key
challenge and significantly varies with respect to the applied
potential. Here, we introduce a pulsed-bias electrochemical
reduction process for the conversion of CO2 on polycrystalline
Cu catalyst, displaying high selectivity for CO formation over
other carbon products. A few previous studies have employed a
square wave potential with 3−5 s pulses on Cu in an attempt to
Received: March 23, 2016
Revised: June 5, 2016
Published: June 8, 2016

© 2016 American Chemical Society 4739 DOI: 10.1021/acscatal.6b00857

ACS Catal. 2016, 6, 4739−4745
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Figure 1. CO2 reduction performance of Cu catalyst without pulsing. (a) Schematic diagram of customized electrochemical cell. (b) Current density
vs potential (J-E) curve for Cu in CO2-saturated 0.1 M KHCO3 solution. (c) Chronoamperometry (CA) analysis at different applied potentials (vs
RHE) and (d) the corresponding measured faradaic efficiency (F.E.) for each product.
prevent catalyst poisoning,17 but the product distribution was
only moderately affected, permitting a modest enhancement in
the faradaic efficiency of CH4 and C2H4 at high cathodic
potentials. These results are significantly different than
investigated herein using pulses in the millisecond time regime
in which transient phenomena were observed to be increasingly
dominant and the CO2RR product selectivity was completely
different. Interestingly, the proposed method also offers a novel
route for tuning the ratio of H2 and CO (i.e., syngas) at a given
applied potential by varying the pulse time. The selectivity
toward syngas is attributed to the pulse-induced oxidation/
reduction of the Cu surface and the constantly shifting electrical
double layer, which leads to CO formation over other carbon
products (e.g., methane or ethylene). The ability to translate
CO2 into a tunable syngas (H2+CO) composition, which can
be used in a variety of different subsequent catalytic
transformation processes,4b,18 could facilitate the industrializa-
tion of the CO2 electrochemical reduction process catalyzed by
an earth abundant material.
2. EXPERIMENTAL SECTION
2.A. Electrochemical Measurements. All experiments
used polycrystalline Cu foil (99.99%, Alfa Aesar) as working
electrodes. Prior to electrochemical experiments, the Cu foil
was chemically cleaned with 1.0 M HCl solution to remove the
surface oxide and adsorbed impurities. Cu samples were then
rinsed with isopropyl alcohol and DI water. CO2 electro-
reduction studies were performed using a custom-made,
gastight, two-compartment polycarbonate electrochemical cell
(Figure 1a). The cell was designed with a large active
electrocatalyst area (∼5 cm2) relative to a minimal electrolyte
volume (7 mL catholyte), with well-dispersed, uniform CO2
reactant to maximize carbon product concentration and
faradaic efficiency, which helps in the detection of gaseous
and liquid products with high sensitivity as demonstrated
previously.7e An anion exchange membrane (Selemion AMV)
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separated the cathode and anode compartments to prevent
oxidation of the reduction products at the anode. The cathode
compartment contained a gas bubbler at the bottom, a port to
position the Ag/AgCl (3.0 M KCl) reference electrode in the
center, and a wide window for the catalyst working electrode.
The CO2 (99.99%, Specialty Gases) was injected into the
catholyte at a flow rate of 20 sccm using a calibrated mass flow
controller (MKS Instruments). The anode compartment
contained a Pt mesh counter electrode and was also actively
bubbled with CO2 during measurements to maintain a uniform
cell pH of 6.8. All CO2 reduction experiments were carried out
in CO2-saturated 0.1 M KHCO3 (99.99%, Sigma-Aldrich)
aqueous solution at room temperature (298 K). A potentiostat
(Biologic SP-200) with electrochemical impedance spectrosco-
py (EIS) was used for all measurements. The potentials were
recorded using an Ag/AgCl (3.0 M KCl) reference electrode
and reported on a reversible hydrogen electrode (RHE) scale
according to VRHE = VAg/AgCl + 0.210 + 0.059*pHsoln.19 The
solution pH was measured to be 6.8. Potentiostatic EIS
measurements were performed before every CO2RR experi-
ment to determine the uncompensated solution resistance, Ru,
and the potentiostat subsequently compensated for 85% of Ru
during electrolysis. The current densities were determined
relative to geometric projected catalyst area throughout this
study.
2.B. Product Analysis. CO2 reduction products were
measured by gas chromatography (GC, SRI 8610) and nuclear
magnetic resonance (NMR, Bruker 400 MHz) for the gas and
liquid products, respectively. Both instruments were calibrated
with standard gases or liquid solutions. For real-time gas phase
product analysis, the outlet of the cathode compartment was
connected to the GC inlet. The GC system used an automatic
valve injection (1 mL sample) and a thermal conductivity
detector (TCD) and flame ionization detector (FID). Ultrahigh
purity nitrogen (99.99%, Specialty Gases) was used as the
carrier gas for all experiments and was chosen to enable
DOI: 10.1021/acscatal.6b00857
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accurate hydrogen quantification. The first gas sample was
injected after 5 min of potentiostatic CO2 reduction, followed
by three additional GC measurements at 18 min intervals. In
addition, NMR spectroscopy was used to analyze and quantify
the products in the liquid phase by performing 1H NMR
experiments. Samples were prepared by mixing D2O and
electrolyte aliquots in a 1:1 volume ratio. Dimethyl sulfoxide
(DMSO) was added at a known low concentration for internal
calibration. Faradaic efficiency (F.E.) was calculated for the
chronoamperometric measurements without pulsed bias by
determining the charge required to produce the measured
product concentration and dividing by the total charge passed
during the time the sample underwent electrolysis. To ensure a
steady state concentration in the output stream during product
quantification, the first GC measurement (at 5 min) was
excluded, and the following three GC measurements (at 23, 41,
and 59 min) were used to determine an average faradaic
efficiency.
C. Catalyst Characterization. A scanning electron micro-
scope (FEI NOVA nano-SEM 600) was used to study the
surface morphology of the Cu foil. The catalyst surface
properties before and after measurement were characterized
with X-ray photoelectron spectroscopy (XPS) with a VG
Scientific MultiLab 3000 custom-built UHV system (with Cu−
Kα radiation). X-ray diffraction analysis was done by using HR
XRD Bruker D8 instrument.
3. RESULTS
3.A. CO2 Reduction without Pulsed Bias. The chemical
surface cleaning step used before every experiment was a simple
and effective method to remove the oxide layer and other
impurities present on the Cu surface (Figures S1 and S2). SEM
analysis of cleaned Cu films showed featureless surface
morphology and a lack of physically adsorbed particles. Further
elemental analysis by XPS also confirmed the absence of any
metal impurities within the XPS detection limit (Figure S2).
Figure 1b shows the current density vs potential (J-E)
polarization curve for CO2RR obtained by sweeping the
potential between +0.6 and −1.2 V vs RHE at a scan rate of 20
mV s−1. A similar polarization curve was obtained in Ar-
saturated electrolyte, in which case Cu yields only H2 product
(Figure S4). The observed CO2 reduction onset potential
(−0.63 V vs RHE) and measured current density (∼17 mA
cm−2) at −1.2 V vs RHE are consistent with the current density
reported previously for polycrystalline Cu in CO2-saturated 0.1
M KHCO3 solution.7e Chronoamperometry (CA) experiments
were performed at potentials varying from −0.65 to −1.15 V vs
RHE at 50 mV intervals for 60 min at each potential (Figure
1c). Figure 1d shows the average faradaic efficiencies (F.E.) for
all identified major products as a function of applied potential
(shown in Table S1). At low potential (positive of −0.90 V vs
RHE) H2, CO, and HCOOH were the major products. In this
region, hydrogen evolution is kinetically dominant, and the
faradaic efficiency of H2 formation remained high, varying from
96.4% to 53.5% at −0.65 V and −0.90 V vs RHE, respectively.
At higher applied potential (negative of −0.90 V vs RHE), the
total current attributable to CO 2 reduction increased
significantly, with the faradaic efficiency of CO2RR higher
than hydrogen evolution in the studied potential range.
The faradaic efficiency of H2 formation reached a minimum
of 26.3% at −1.05 V vs RHE, where CH4 and C2H4 were the
major carbonaceous products. The observed values and trend in
the product selectivity match well with previously reported
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results on Cu foil catalyst in aqueous electrolyte within the
limited cathodic potential range.7e,20
3.B. CO2 Reduction with Pulsed Bias. Figure 2a
generically illustrates the potential waveform applied during
Figure 2. CO2 reduction performance of Cu catalyst with pulsing. (a)
Illustrative pulse in which the applied potential was alternated between
an anodic rest potential, Ea (0.6 V vs RHE), for a time period of ta, and
the cathodic working potential, Ec, for a time period of tc. (b−d)
Reduction products in percentage (%) of charge required at different
applied potentials (Ec), (b) −1.05 V, (c) −1.0 V, and (d) −0.95 V vs
RHE, as a function of pulse time, tc. For (b−d), ta = tc for each
measurement, and CA denotes chronoamperometric conditions at the
cathodic working potential without pulsed bias.
the pulsed-bias electrolysis experiments. In this method, the
applied bias was alternated between an anodic rest potential, Ea,
at +0.61 V vs RHE (0.0 V vs Ag/AgCl), for a time ta, and a
cathodic working potential, Ec, negative of the CO2 onset
potential (−0.63 V vs RHE) for a time tc. Other than the
applied potential pulse mode, experimental conditions were
identical to previous experiments. Due to the discrete, step-like
switch between Ea and Ec, sharp transient current spikes
occurred immediately after the application of both Ea and Ec
throughout the pulsed potential waveform (Figure S7).
Deconvolution of the faradaic reaction current from the
nonfaradaic transient current processes during pulsed elec-
trolysis was not straightforward and deemed too unreliable for
accurately reporting faradaic efficiencies of products. CO2
reduction product selectivity was therefore reported for each
species as the charge required to create that amount of product
as a percentage of the total charge required to create all
detected products (rather than the total charge passed during
the experiment). Figure 2b−d shows the variation in product
selectivity at Ec of −1.05, −1.00, and −0.95 V vs RHE while
varying pulse time tc from 0 to 100 ms with equivalent time
periods of ta. Without pulsed bias, CH4, C2H4, and H2 were the
main products in this potential window (Figure 1d), but the
application of the pulsed potential strongly favored the
direction of charge to CO and H2 in a ratio dependent on
the pulse time. At 100 ms pulse times some hydrocarbon
products were still detected, but at pulse times <50 ms, CH4
and C2H4 products were completely suppressed with CO as the
only detectable carbonaceous product. Under these conditions,
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CO formation peaked at 50 ms pulse times with a ∼1:1 molar
ratio of H2 to CO. Shorter pulse times led to H2 production
increasingly being favored over CO formation, reaching ∼97%
H2 for 10 ms pulse periods. For all pulsed-bias conditions
tested, no liquid phase products were detected (Figure S8), and
these species are therefore omitted from the graphs for CO2
reduction under pulsed bias.
Figure 3a shows the product selectivity for pulsed-bias CO2
reduction at a constant tc (50 ms) while varying ta from 0 to
attained a maximum value of ∼64% at ta = 80 ms and remained
consistent up through ta = 130 ms. By varying the pulse times
for a given cathodic working potential (i.e., −1.0 V vs RHE),
CO production was thus promoted relative to H2 production
from a molar ratio of ∼1:10 under potentiostatic conditions to
16:9 (CO:H2) with tc = 50 ms and ta = 80 ms. The CO and H2
formation rates with varying ta pulse time are given in Figure
3b. As expected, as the rest pulse time ta became longer with
respect to the working pulse time tc at sufficiently cathodic
potentials for reduction, the overall product formation rate
decreased. Although the total reduction rate decreased
modestly by ∼20% between potentiostatic and peak CO
pulsing conditions (tc = 50 ms, ta = 80 ms), CO formation
demonstrated the opposite trend and increased from ∼0.5
nmol s−1 cm−2 to ∼5.3 nmol s−1 cm−2 at the same conditions.

Figure 3. Selectivity dependence on ta. (a) Product charge percentage
at −1.0 V vs RHE with tc = 50 ms and different ta pulse times. (b)
Product formation rate with varying ta pulse times.
140 ms at a cathodic working potential, Ec, of −1.0 V vs RHE.
For a short rest pulse of ta = 10 ms, the GC measured ∼97% H2
and ∼3% CO, while CH4 and C2H4 were out of the detection
range. The introduction of this short pulse thus strongly
reduced the rate of CO2 reduction. However, with longer pulses
of ta > 10 ms, CO as a percentage of the product increased and
4. DISCUSSION
The chronoamperometric experiments without a pulsed bias
show the well-established CO2RR product distribution as a
function of applied potential on a Cu foil electrocatalyst in
aqueous electrolyte (Figure 1d).7e Theoretical and experimen-
tal studies have elucidated numerous reaction mechanisms and
pathways to account for the product selectivity behavior on Cu
surfaces.7e,13c,20,21 The CO2 electroreduction mechanism on Cu
is a complex phenomenon with multiple proton-coupled
electron-transfer steps and possible reaction pathways depend-
ent upon the formation of various intermediate species,
involving both electrochemical as well as nonelectrochemical
steps (e.g., adsorption, dimerization, etc.).21a,d It is, however,
generally accepted that the unique ability of Cu electrocatalysts

Figure 4. Catalyst surface effects during pulsed-bias electrolysis. (a) SEM image of a Cu foil after pulsed-biased conditions at a cathodic working
potential of −1.0 V vs RHE. (b) XPS spectra on a Cu foil electrode that was pristine (Cu), tested under chronoamperometric conditions (Cu CA),
and tested under pulsed-bias conditions with 50 ms pulses (Cu 50 ms) and corresponding (c) XRD spectra. (d) Schematic diagram representing the
proposed mechanistic effects on CO2 reduction from the pulsed-bias method as compared to potentiostatic electrolysis. Under potentiostatic
conditions, bound CO* can desorb to form CO, further reduce to CH4, or react with an adjacent CO* and reduce to C2H4. Under pulsed-bias
conditions in this time regime, it is proposed that anodic current during the Ea pulse oxidizes the surface with water which is subsequently reduced
back to a nanoscopically roughened metal surface as in (a) from cathodic current flow during the Ec pulse. Adsorbed CO2 during the Ec pulse is
reduced to CO*, which is proposed to primarily desorb to CO owing to both the changed catalyst surface active sites relative to the pure
polycrystalline Cu as well as the changing electric field due to the double layer charging/discharging.

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to form significant amounts of hydrocarbon products is due to a
surface binding energy which leads to near-optimal stability of
the adsorbed CO intermediate species which is a precursor to
the formation of higher carbon products (e.g., methane,
ethylene, and methanol). Thus, at increasingly reductive
potentials, CO2RR on Cu promotes hydrocarbon products
over CO formation (Figure 1d).7e
As seen in Figure 2, the application of a pulsed bias rather
than a potentiostatic bias led to a drastically altered CO2RR
product distribution at a Cu electrode. The pulses switched
between the reductive working potential and a rest potential
below the thermodynamic potential for CO2 reduction or
hydrogen evolution. The introduction of the pulsed potential
waveform changed the reaction mechanism, directing more
charge at the tested working potentials to CO formation and
suppressing other reduction products. In particular, for pulse
durations of tc = ta ≥ 50 ms, the percent of charge passed to
produce H2 decreased and the CO2 reduction products
increased relative to the potentiostatic condition, peaking at a
∼ 1:1 ratio at 50 ms pulses. This result is consistent with the
pulsed-bias approach easing the effects of mass-transport
limitations on the reaction. In potentiostatic mode, diffusion
of dissolved CO2 to the catalyst surface limits CO2RR and
convolutes the kinetic competition with hydrogen evolution,
promoting H2. Pulsed mode, on the other hand, provides
additional time for CO2 diffusion. During periods at the Ec
potential, CO2 reduction can proceed in kinetic competition
with hydrogen evolution. During periods at the Ea potential
below either thermodynamic reaction potential, neither
reduction reaction would be predicted to occur, providing
time for CO2 from the bulk electrolyte to diffuse to the catalyst
surface for reaction during the next Ec pulse. This type of pulse
voltammetry to mitigate mass-transport limitations in a reaction
has been successfully applied in other electrochemical systems,
for instance as a technique to enable conformal electro-
deposition on microstructured high-aspect ratio surfaces.22
Although the pulsed-bias effect on mass-transport limitations
explains the promotion of CO2 reduction over H2 formation,
this theory does not account for the observed mechanistic
change to favor CO over other carbonaceous products nor the
decrease in CO production at pulse times <50 ms.
Further investigation was necessary to elucidate the
mechanistic shift in CO2RR under millisecond potential pulses.
One hypothesized reason for the selective formation of CO
under pulsed-bias conditions was that hydrocarbons formed at
reductive conditions during the Ec pulse could be oxidized from
transient anodic currents during the Ea pulse. To examine this,
we performed control experiments by introducing CH4 at 20
sccm without CO2 under pulsed-bias reaction conditions. The
resulting absence of any CO peak in the GC spectra suggested
that CO formation was only due to CO2 reduction rather than
the conversion of any hydrocarbons formed in situ. We cannot,
however, exclude the possibility of the oxidation of surface
adsorbed hydrocarbon intermediates during pulsed-bias elec-
trolysis conditions. A possible change to the Cu catalyst surface
induced by pulsed-bias conditions could also be responsible for
the changed CO2RR product branching ratio. Figure 4a shows
the Cu catalyst surface after 60 min of electrolysis under pulsed-
bias conditions with a cathodic working potential of −1.0 V vs
RHE. The catalyst surface displayed increased nanoscopic
roughness compared to a freshly cleaned Cu foil electrode
(Figures S1 and S10). Figure 4b shows the surface chemical
analysis by XPS of the O 1s spectra for pristine Cu, a Cu foil
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after potentiostatic electrolysis, and a Cu foil after pulsed-bias
electrolysis. The additional peak present at 530 eV after pulsed-
bias electrolysis for 60 min, which was observed for each set of
pulse times tested and ending on either potential, corresponds
to CuOx (Figure S11).23 The results are further supported by
XRD analysis where characteristic peaks of CuOx are clearly
visible (Figure 4c). The pulsed-bias condition is thus
interpreted to cause the in situ formation of CuO and Cu2O
surface layers, perhaps due to anodic current flow during the Ea
pulse. Subsequent electrochemical reduction of the oxide layer
during the Ec pulse likely leads to the surface roughening,
similar to the intentional nanostructuring that arises in oxide-
derived Cu catalysts for CO2RR.24 Furthermore, oxide-derived
Cu as either foils24 or highly dense nanowires14 has shown high
CO2RR selectivity toward CO formation as compared to
standard polycrystalline Cu. The enhanced CO faradaic
efficiency was attributed to the improved stabilization of the
CO2•− intermediate on the high surface area of oxide-derived
Cu nanowire arrays.14 It should also be noted that the presence
of an oxide layer during the Ec pulse likely further contributes
to the CO selectivity. Copper oxide surfaces have been found in
some cases to favor CO formation in comparison to other
carbon products (e.g., CH4 and C2H4).14,24,25 For instance, Lan
et al., reported CO as the main product on Cu(core)/
CuO(shell) structures even at high applied potential (−1.73 V
vs Ag/AgCl).26 The morphological and chemical trans-
formation of the Cu catalyst surface under the transient
conditions of pulsed-bias electrolysis thus leads to desorption of
the CO species before it can undergo further reduction to
hydrocarbon products. Thus, while the kinetics for CO2
conversion to CO are sufficiently fast for an appreciable
reaction rate during the millisecond pulse time regime, sluggish
kinetics for further reduction of CO to CH4 could be inhibiting
hydrocarbon formation under these pulse conditions.
On the millisecond time scale for pulses used in this work,
transient current spikes after the step-change in potential were
significant and prevented the establishment of a steady-state
reduction current within a given pulse. This type of transient
electrochemical current is commonly associated with a
nonfaradaic process, usually due to a capacitive charging
current rather than faradaic reaction current. The capacitive
behavior primarily arises from the charging and discharging of
the electrical double layer, or Helmholtz layer, at the electrode
surface.19 We speculate that the changing local electric field
near the catalyst surface during the charging and discharging of
the electrical double layer could have a significant effect on the
binding energy experienced by adsorbed reaction intermediates.
A nonideal binding energy during the transient charging current
could thus lead to desorption of the critical CO intermediate
before further reduction to hydrocarbon species can occur. The
changing Helmholtz layer effect is consistent with the near-total
directing of CO2 reduction current to CO product under
pulsed bias. Furthermore, this effect is consistent with the
observed behavior at shorter pulse times (i.e., <50 ms), in
which hydrogen evolution was increasingly promoted over CO
formation (Figure 2). At shorter pulse times, the nonfaradaic
capacitive current became increasingly dominant, and the
rapidly changing electrical double layer may inhibit the binding
of CO2 before it can even be reduced to CO. Figure 4d
illustrates the changes to the mechanistic pathway of CO2RR
on Cu between potentiostatic and pulsed-bias electrolysis due
to the combined effects of a surface oxide and a shifting
electrical double layer as proposed in this work.
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The dependence of the electrolysis product selectivity on the
pulse time periods provides an electronic technique for tuning
the H2 to CO ratio at a specified working potential. The
production of syngas of varying composition can therefore be
controlled without changing the applied working voltage, and
hence the overpotential, of the reaction. As Figures 2 and 3
demonstrate, syngas can be produced without significant
byproducts with CO ranging from ∼3% to ∼64% by changing
the pulse times within a range of 10−80 ms. The syngas
production rate, however, decreased as the anodic rest potential
Ea time became a greater fraction of the overall potential
waveform (Figure 3b). The decline in total product formation
can be attributed to the drop in the fraction of time (i.e., tc/(tc
+ ta)) responsible for CO2 electroreduction. Because the
applied potential Ea during ta is positive of the thermodynamic
potential for both CO2 reduction and hydrogen evolution,
syngas production does not occur within this period. Pulsed-
bias electrochemical CO2 reduction thus holds promise for
industrial applications requiring syngas. Syngas can either be
used directly as a fuel or as a feedstock for the synthesis of
numerous, energy-dense chemicals including synthetic natural
gas, liquid hydrocarbons via the Fischer−Tropsch process, and
value-added chemicals through the hydroformylation process.18
In each syngas conversion process, a specific ratio of H2 to CO
is required in the process feed gas to optimize the product
yield. The pulsed-bias technique could be applied to correct
and optimize the syngas composition in real time without
degrading the electrolysis efficiency. The pulsing method could
also provide versatility to a centralized CO2 reduction system
meant to supply syngas to a variety of chemical processes. One
current commercial technology for adjusting the H2:CO syngas
ratio involves a system of specialized membranes with flow
control valves.27 The pulsed-bias electrolysis method, in
comparison, has the advantage of tuning the syngas ratio at
the source without the need for any capital-intensive hardware
or additional energy expenditures.
5. CONCLUSION
Electrochemical CO 2 reduction at Cu electrodes was
characterized with full product quantification in aqueous
electrolyte under both potentiostatic and pulsed-bias con-
ditions. The introduction of a square-wave applied potential to
the Cu catalyst drastically altered the CO2RR product
selectivity, producing only H2 and CO in ratios strongly
dependent on the pulse time. The product syngas H2:CO molar
ratio varied between ∼32:1 and 9:16 with working pulse times
of 10 and 50 ms, respectively. Several complex phenomena are
likely interacting during the transient electrochemical process
to create the observed behavior. Increased CO2 reduction
relative to hydrogen evolution at longer pulse times is evidence
that the pulse waveform enhanced the mass-transport of
dissolved CO2 molecules to the electrode surface. In situ
oxidation and reduction of the Cu surface during transient
anodic/cathodic currents is suspected to create a changing
surface of nanostructured Cu oxide and oxide-derived Cu, both
of which have been demonstrated to favor CO production over
hydrocarbons. The transient, capacitive charging and discharg-
ing of the electrical double layer at the electrode surface is also
proposed to lead to an unstable local electric field at the catalyst
surface on the millisecond scale that inhibits the binding of key
intermediate species and prevents the subsequent reduction
steps that lead to hydrocarbon products. The results highlight a
unique strategy for tunable syngas production on cost-effective
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Cu catalysts. The pulsed waveform dependency of the H2 to
CO ratio permits the syngas product composition to be easily
adjusted in real time by changing the pulse duration and/or
cathodic working potential. This technique provides versatility
for integrating electrochemical CO2 reduction into industrial
processes for the synthesis of fuels or value-added chemicals at
a large scale.
■ ASSOCIATED CONTENT
* Supporting Information
S
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acscatal.6b00857.
Additional information about the morphological, ele-
mental, and electrochemical characterization results
(PDF)
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: joshua.spurgeon@louisville.edu.
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
The authors acknowledge financial support from the Kentucky
Department for Energy Development and Independence grant
#PON2 127 1500002410. The authors also acknowledge
support from the Conn Center for Renewable Energy Research
at the University of Louisville.
■
REFERENCES
(1) (a) Davis, S. J.; Caldeira, K.; Matthews, H. D. Science 2010, 329,
1330−1333. (b) Hall-Spencer, J. M.; Rodolfo-Metalpa, R.; Martin, S.;
Ransome, E.; Fine, M.; Turner, S. M.; Rowley, S. J.; Tedesco, D.; Buia,
M.-C. Nature 2008, 454, 96−99. (c) Hoffert, M. I.; Caldeira, K.; Jain,
A. K.; Haites, E. F.; Harvey, L. D. D.; Potter, S. D.; Schlesinger, M. E.;
Schneider, S. H.; Watts, R. G.; Wigley, T. M. L.; Wuebbles, D. J.
Nature 1998, 395, 881−884.
(2) Mikkelsen, M.; Jorgensen, M.; Krebs, F. C. Energy Environ. Sci.
2010, 3, 43−81.
(3) Sanna, A.; Uibu, M.; Caramanna, G.; Kuusik, R.; Maroto-Valer,
M. M. Chem. Soc. Rev. 2014, 43, 8049−8080.
(4) (a) Daza, Y. A.; Kent, R. A.; Yung, M. M.; Kuhn, J. N. Ind. Eng.
Chem. Res. 2014, 53, 5828−5837. (b) Xiaoding, X.; Moulijn, J. A.
Energy Fuels 1996, 10, 305−325.
(5) (a) Kumar, B.; Brian, J. P.; Atla, V.; Kumari, S.; Bertram, K. A.;
White, R. T.; Spurgeon, J. Catal. Today 2016, 270, 19−30. (b) Qiao, J.;
Liu, Y.; Hong, F.; Zhang, J. Chem. Soc. Rev. 2014, 43, 631−675.
(c) Costentin, C.; Robert, M.; Saveant, J.-M. Chem. Soc. Rev. 2013, 42,
2423−2436. (d) Jitaru, M.; Lowy, D. A.; Toma, M.; Toma, B. C.;
Oniciu, L. J. Appl. Electrochem. 1997, 27, 875−889.
(6) (a) Kumar, B.; Llorente, M.; Froehlich, J.; Dang, T.; Sathrum, A.;
Kubiak, C. P. Annu. Rev. Phys. Chem. 2012, 63, 541−569. (b) Martin,
A. J.; Larrazabal, G. O.; Perez-Ramirez, J. Green Chem. 2015, 17,
5114−5130. (c) Kondratenko, E. V.; Mul, G.; Baltrusaitis, J.;
Larrazabal, G. O.; Perez-Ramirez, J. Energy Environ. Sci. 2013, 6,
3112−3135.
(7) (a) Azuma, M.; Hashimoto, K.; Hiramoto, M.; Watanabe, M.;
Sakata, T. J. Electrochem. Soc. 1990, 137, 1772−1778. (b) Rosen, B. A.;
Salehi-Khojin, A.; Thorson, M. R.; Zhu, W.; Whipple, D. T.; Kenis, P.
J. A.; Masel, R. I. Science 2011, 334, 643−644. (c) Feng, X.; Jiang, K.;
Fan, S.; Kanan, M. W. J. Am. Chem. Soc. 2015, 137, 4606−4609.
(d) Zhu, W.; Michalsky, R.; Metin, Ö .; Lv, H.; Guo, S.; Wright, C. J.;
Sun, X.; Peterson, A. A.; Sun, S. J. Am. Chem. Soc. 2013, 135, 16833−
16836. (e) Kuhl, K. P.; Cave, E. R.; Abram, D. N.; Jaramillo, T. F.
Energy Environ. Sci. 2012, 5, 7050−7059. (f) Kauffman, D. R.; Alfonso,
DOI: 10.1021/acscatal.6b00857
ACS Catal. 2016, 6, 4739−4745
ACS Catalysis Research Article

D.; Matranga, C.; Qian, H.; Jin, R. J. Am. Chem. Soc. 2012, 134,
10237−10243.
(8) Chen, Y.; Kanan, M. W. J. Am. Chem. Soc. 2012, 134, 1986−1989.
(9) Ramos Sende, J. A.; Arana, C. R.; Hernandez, L.; Potts, K. T.;
Keshevarzk, M.; Abruna, H. D. Inorg. Chem. 1995, 34, 3339−3348.
(10) (a) Kumar, B.; Asadi, M.; Pisasale, D.; Sinha-Ray, S.; Rosen, B.
A.; Haasch, R.; Abiade, J.; Yarin, A. L.; Salehi-Khojin, A. Nat. Commun.
2013, 4, 2819. (b) Liu, Y.; Chen, S.; Quan, X.; Yu, H. J. Am. Chem. Soc.
2015, 137, 11631−11636.
(11) Gattrell, M.; Gupta, N.; Co, A. J. Electroanal. Chem. 2006, 594,
1−19.
(12) Lu, Q.; Rosen, J.; Zhou, Y.; Hutchings, G. S.; Kimmel, Y. C.;
Chen, J. G.; Jiao, F. Nat. Commun. 2014, 5, 3242.
(13) (a) Guo, X.; Zhang, Y.; Deng, C.; Li, X.; Xue, Y.; Yan, Y.-M.;
Sun, K. Chem. Commun. 2015, 51, 1345−1348. (b) Nie, X.; Esopi, M.
R.; Janik, M. J.; Asthagiri, A. Angew. Chem., Int. Ed. 2013, 52, 2459−
2462. (c) Durand, W. J.; Peterson, A. A.; Studt, F.; Abild-Pedersen, F.;
Norskov, J. K. Surf. Sci. 2011, 605, 1354−1359.
(14) Raciti, D.; Livi, K. J.; Wang, C. Nano Lett. 2015, 15, 6829−6835.
(15) Reske, R.; Mistry, H.; Behafarid, F.; Roldan Cuenya, B.; Strasser,
P. J. Am. Chem. Soc. 2014, 136, 6978−6986.
(16) Sen, S.; Liu, D.; Palmore, G. T. R. ACS Catal. 2014, 4, 3091−
3095.
(17) (a) Yano, J.; Morita, T.; Shimano, K.; Nagami, Y.; Yamasaki, S. J.
Solid State Electrochem. 2007, 11, 554−557. (b) Ishimaru, S.;
Shiratsuchi, R.; Nogami, G. J. Electrochem. Soc. 2000, 147, 1864−
1867. (c) Yano, J.; Yamasaki, S. J. Appl. Electrochem. 2008, 38, 1721−
1726. (d) Nogami, G.; Itagaki, H.; Shiratsuchi, R. J. Electrochem. Soc.
1994, 141, 1138−1142.
(18) Wilhelm, D. J.; Simbeck, D. R.; Karp, A. D.; Dickenson, R. L.
Fuel Process. Technol. 2001, 71, 139−148.
(19) Bard, A. J.; Faulkner, L. R. Electrochemical Methods:
Fundamentals and Applications, 2nd ed. ed.; John Wiley & Sons: 2001.
(20) Hori, Y.; Murata, A.; Takahashi, R. J. Chem. Soc., Faraday Trans.
1 1989, 85, 2309−2326.
(21) (a) Kortlever, R.; Shen, J.; Schouten, K. J. P.; Calle-Vallejo, F.;
Koper, M. T. M. J. Phys. Chem. Lett. 2015, 6, 4073−4082. (b) Peterson,
A. A.; Abild-Pedersen, F.; Studt, F.; Rossmeisl, J.; Norskov, J. K. Energy
Environ. Sci. 2010, 3, 1311−1315. (c) Nie, X.; Esopi, M. R.; Janik, M.
J.; Asthagiri, A. Angew. Chem., Int. Ed. 2013, 52, 2459−2462.
(d) Schouten, K. J. P.; Kwon, Y.; van der Ham, C. J. M.; Qin, Z.;
Koper, M. T. M. Chem. Sci. 2011, 2, 1902−1909.
(22) Sun, J. J.; Kondo, K.; Okamura, T.; Oh, S. J.; Tomisaka, M.;
Yonemura, H.; Hoshino, M.; Takahashi, K. J. Electrochem. Soc. 2003,
150, G355−G358.
(23) (a) Liu, P.; Li, Z.; Cai, W.; Fang, M.; Luo, X. RSC Adv. 2011, 1,
847−851. (b) Diaz-Droguett, D. E.; Espinoza, R.; Fuenzalida, V. M.
Appl. Surf. Sci. 2011, 257, 4597−4602.
(24) Li, C. W.; Kanan, M. W. J. Am. Chem. Soc. 2012, 134, 7231−
7234.
(25) (a) Xie, J.; Huang, Y.; Yu, H. Front. Environ. Sci. Eng. 2015, 9,
861−866. (b) Kas, R.; Kortlever, R.; Milbrat, A.; Koper, M. T. M.;
Mul, G.; Baltrusaitis, J. Phys. Chem. Chem. Phys. 2014, 16, 12194−
12201.
(26) (a) Lan, Y.; Gai, C.; Kenis, P. J. A.; Lu, J. ChemElectroChem
2014, 1, 1577−1582. (b) Lan, Y.; Ma, S.; Lu, J.; Kenis, P. J. A. Int. J.
Electrochem. Sci. 2014, 9, 7300−7308.
(27) Generon Innovative Gas Systems. http://www.generon.com/
pdf/Syngas-H2-CO-Ratio-Adjustment-CO-Recovery.pdf (accessed
June 1, 2016).

4745 DOI: 10.1021/acscatal.6b00857

ACS Catal. 2016, 6, 4739−4745