Article

pubs.acs.org/Langmuir

Switching the Reaction Course of Electrochemical CO2 Reduction

with Ionic Liquids
Liyuan Sun,† Ganganahalli K. Ramesha,‡ Prashant V. Kamat,*,†,‡,§ and Joan F. Brennecke*,†
†
Department of Chemical and Biomolecular Engineering, ‡Radiation Laboratory, and §Department of Chemistry and Biochemistry,
University of Notre Dame, Notre Dame, Indiana 46556, United States
*
S Supporting Information

ABSTRACT: The ionic liquid 1-ethyl-3-methylimidazolium

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bis(trifluoromethylsulfonyl)imide ([emim][Tf2N]) offers new

ways to modulate the electrochemical reduction of carbon
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dioxide. [emim][Tf2N], when present as the supporting

electrolyte in acetonitrile, decreases the reduction over-
potential at a Pb electrode by 0.18 V as compared to
tetraethylammonium perchlorate as the supporting electrolyte.
More interestingly, the ionic liquid shifts the reaction course
during the electrochemical reduction of carbon dioxide by
promoting the formation of carbon monoxide instead of
oxalate anion. With increasing concentration of [emim]-
[Tf2N], a carboxylate species with reduced CO2 covalently
bonded to the imidazolium ring is formed along with carbon monoxide. The results highlight the catalytic effects of the medium
in modulating the CO2 reduction products.

1. INTRODUCTION tional toxic and volatile organic solvents in many chemical

The steadily increasing atmospheric concentration of carbon
dioxide (CO2), a major greenhouse gas, mainly generated from
burning of fossil fuels, and its potential impact on climate has
been the topic of much discussion.1−4 On the other hand, CO2
is recognized as a naturally abundant and inexpensive carbon
source for the production of fuels and feed stocks for a variety
of chemical syntheses in industry.2,4 Therefore, an attractive
way to mitigate increasing atmospheric CO2 concentrations is
through conversion of CO2 into fuels and useful chemicals
using carbon-neutral energy resources.4 Approaches such as
chemical, thermochemical, photochemical, biochemical, and
electrochemical reduction methods have been investigated to
achieve CO2 conversion.1,5−11 Of these methods, electro-
chemical reduction of CO2 is considered to be attractive
because of its higher achievable conversion efficiency, its
product selectivity, and its potential to store electrical energy
that is extracted from renewable energy sources like the
sun.4,12,13 CO2 is thermodynamically stable and kinetically
inert; the main hurdle in the electrochemical CO2 reduction lies
in the first step, the one-electron reduction of CO2. This
activation of CO2 to form an anion radical (CO2−•) requires an
unusually high reduction potential of −1.9 V vs NHE,14
associated with an overpotential that is dependent on the
electrode and medium.11,13,15−17 Efforts have been made to
achieve CO2 reduction at lower electrochemical potentials, e.g.,
using pyridinium-based homogeneous catalysts.18
Due to their low volatility, nonflammability, good solvating
ability, and good thermal and chemical stability, ionic liquids
(ILs) have been regarded as “green” alternatives for conven-
processes. Additionally, the high solubility of CO2 in ILs,19−21
intrinsic ionic conductivity, and wide potential windows make
ILs attractive media for electrochemical reduction of CO2.
Recently, Rosen et al. reported the effective lowering of the
reduction overpotential for CO2 conversion into CO at Pt and
Ag electrodes in an aqueous solution of the IL 1-ethyl-3-
methylimidazolium tetrafluoroborate ([emim][BF4]). They
proposed that the effectiveness of this newly observed catalytic
reduction relies on the ability of the IL to lower the energy
barrier for the formation of CO2−• through the formation of a
complex.11 Wipple et al. also proposed that the overpotential of
CO2 reduction could be lowered by stabilizing the intermediate
CO2−• using a suitable catalyst.4
Electrochemical reduction is a convenient approach to carry
out reduction of CO2 in a controlled way. The product
distribution varies depending on the type of metal electrodes
employed in a certain electrolyte. For example, oxalate has been
widely reported as the major product of CO2 reduction at a Pb
electrode in nonaqueous media.12,22−24 Also, Pb is considered
to be an inert electrode material that does not interfere with the
reduction of CO2 and the competing pathways for product
formation.17 Here we investigate the role that the IL 1-ethyl-3-
methylimidazolium bis(trifluoromethylsulfonyl)imide ([emim]-
[Tf2N], shown in Figure 1) plays as a homogeneous catalyst for
CO2 reduction using electrochemical reduction at a Pb cathode.
Received: March 7, 2014
Revised: May 9, 2014
Published: May 13, 2014

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Figure 1. Structure of the ionic liquid [emim][Tf2N].
Specifically, we seek answers to the following questions: (1)
how does [emim][Tf2N] mediate the product selectivity during
CO2 reduction and (2) how does the mechanism of CO2
reduction switch from oxalate anion to CO in an IL-based
nonaqueous medium?
2. RESULTS AND DISCUSSION
2.1. Voltammetry Study of CO2 Reduction in TEAP/
AcN and [emim][Tf2N]/AcN at a Pb Working Electrode.
The cyclic voltammograms (CVs) measured using a Pb cathode
in 0.1 M tetraethylammonium perchlorate/acetonitrile (TEAP/
AcN) and 0.1 M [emim][Tf2N]/AcN are shown in Figure 2.
These voltammograms were recorded at a potential sweep rate
of 50 mV/s at room temperature after the electrolyte solution
was purged with N2 for 30 min to remove dissolved oxygen,
followed by purging with CO2 for another 30 min. Parts a and b
show the reductive scan of N2-saturated and CO2-saturated
electrolyte solutions, respectively. The increased current seen in
the CO2-saturated solutions confirms the ability of Pb electrode
to reduce CO2 to CO2−•.
The onset potential corresponding to the reduction of CO2
in the presence of 0.1 M [emim][Tf2N]/AcN is decreased by
0.18 V compared to that of 0.1 M TEAP/AcN. The onset
potential is −2.30 V in 0.1 M TEAP/AcN and −2.12 V in 0.1
M [emim][Tf2N]/AcN with respect to the reference electrode
(Ag/AgNO3), as seen in Figure 2. Since it is difficult to
establish the exact reduction peak, we selected potentials that
gave a current of 0.6 mA/cm2 for performing reduction of CO2
in acetonitrile. Potentials of −2.40 and −2.25 V (vs Ag/
AgNO3) were employed for CO2 reduction in 0.1 M TEAP/
AcN and 0.1 M [emim][Tf2N]/AcN, respectively, in our
experiments, unless otherwise indicated. This approach of
monitoring the apparent current density at a fixed potential is
consistent with earlier reports.25 The difference in the two
reduction potentials represents the decrease in overpotential in
the [emim][Tf2N]/AcN system compared to TEAP/AcN.
Figure 2. Cyclic voltammograms (CVs) recorded using a Pb working electrode in an electrolyte containing (A) 0.1 M TEAP/AcN and (B) 0.1 M
[emim][Tf2N]/AcN. The CVs were recorded in (a) N2-saturated and (b) CO2-saturated solutions. (Scan rate 50 mv/s. The vertical line in each plot
is the potential employed for electrolysis experiments.)
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2.2. Electrolysis at Controlled Potentials and Product
Analysis. We carried out electrolysis at controlled potentials to
monitor the CO2 reduction products. When the electrolysis was
carried out for 60 min in 0.1 M TEAP/AcN we observed the
formation of a white precipitate. Analysis of the precipitate
using FTIR spectra (see Supporting Information, Figure S3)
confirmed the formation of oxalate as the primary product of
CO2 reduction. Oxalate generated from CO2 reduction in 0.1
M TEAP/AcN was quantified using HPLC (Supporting
Information, Figure S4). The formation of oxalate anion is
the result of dimerization of CO2−•. This selective reduction
product formed at Pb electrodes agrees with earlier
findings.22,23
The oxalate formation was significantly decreased when 0.1
M [emim][Tf2N]/AcN was used as an electrolyte. Efforts were
made to isolate and identify reduction products using 1H and
13
C NMR. In addition, the gaseous reduction product, carbon
monoxide (CO), was analyzed using GC analysis of the head
space samples. The resonance lines of [emim][Tf2N] in the 1H
NMR spectrum were assigned from their multiplet splitting
patterns, as well as comparison with peak assignments for other
[emim]+ ILs whose NMR spectra are available in the
literature.26 The chemical shifts of the protons in [emim]-
[Tf2N] are summarized in Table 1, according to the labeling
Table 1. 1H NMR Chemical Shifts (DMSO, δ, ppm relative
to TMS) of the Pure 1-ethyl-3-methylimidazolium
bis(trifluoromethylsulfonyl)imide ([emim][Tf2N]) and of
the Solution Obtained by CO2 Electrochemical Reduction at
−2.25 V vs Ag/AgNO3 in 0.1 M [emim][Tf2N]/AcN at
Room Temperature, under Atmospheric Pressure for 1 h
no. of H
atom pure [emim][Tf2N] COO−[emim][Tf2N] [emim][Gly]26
7 1.42 1.35 1.41
8 3.85 3.96 3.87
6 4.20 4.48 4.22
5 7.69 7.54 7.75
4 7.77 7.61 7.84
2 9.12 9.68
shown in Figure 3. As is shown in the spectra in Figure 3a−c,
the original resonance lines of pure [emim][Tf2N], with the
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Figure 3. 1H NMR spectra (in DMSO, reference to TMS) of (a) pure [emim][Tf2N], (b) 0.1 M [emim][Tf2N]/AcN after purging CO2 for 30 min,
(c) 0.1 M [emim][Tf2N]/AcN electrolysis solution after 1 h of CO2 reduction, and (d) separated precipitate generated in CO2 reduction. The
schematic representation of the [emim][Tf2N] ion pair with the labeling of the carbon atom used in the assignment is displayed.
exception of the proton on C2, become accompanied by a
corresponding secondary line of lower intensity after CO2
electrochemical reduction is carried out in [emim][Tf2N]/
AcN. The composite spectrum of the electrolysis solution
mixture indicates a substitution reaction at C2 of the
imidazolium ring to form a reacted imidazolium species.
Figure 3d shows the 1H NMR spectrum of a precipitate
generated during the electrolysis of CO2-saturated 0.1 M
[emim][Tf2N]/AcN after it was isolated from the electrolysis
solution mixture, purified, and dissolved in DMSO. The main
resonance lines in this spectrum correspond to the protons of
the new reacted imidazolium species, which we believe to be a
carboxylate complex. The less intense lines at the same
chemical shifts as the pure IL can be attributed to residual
unreacted IL in the precipitate. There have been abundant
literature reports describing carboxylation at the C2 position of
imidazolium-based ILs, triggered by reaction with neutral CO2
molecules.3,27−29 The reaction scheme is shown in Figure 4,
although there is some debate regarding the reversibility of the
reaction. We reason from the spectra in Figure 3 that
electrochemically reduced CO2 is also capable of deprotonating
the imidazolium ring to form a carboxylate species. In addition,
we observe a resonance line at 155.1 ppm in the 13C NMR
spectrum of the CO2-saturated 0.1 M [emim][Tf2N]/AcN
Figure 4. A schematic diagram of the carboxylation of C2 of the
imidazolium ring by CO2. Redrawn according to refs 16−18.
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solution after electrolysis (Supporting Information, Figure S6),
which can be attributed to the carboxylate group covalently
bound to C2 of the imidazolium ring,27 providing further
confirmation that a carboxylate species was formed. It needs to
be pointed out that electrospray ionization (ESI) MS provides
further evidence of the formation of the carboxylate species by
showing a peak with an m/z value of 155.0822 (Supporting
Information, Figure S7). The 1-ethyl-3-methylimidazolium-2-
carboxylate species was quantified on the basis of integration of
peak intensities in the 1H NMR spectra, and CO was quantified
by GC (Supporting Information, Figure S5).
Rosen et al. 10 suggested that an adsorbed neutral
[emimCO2] complex was responsible for lowering the
overpotential for the electrochemical conversion of CO2 to
CO, lending support to the discovery presented here of a 1-
ethyl-3-methylimidazolium-2-carboxylate species in solution
and as a bulk precipitate. From the 1H NMR spectra we
cannot determine if the complex is neutral or negatively
charged. We envision that the [emim]+ cation is deprotonated
to form the neutral carbene (Figure 4). The carbene then reacts
with the reduced CO2−•, which would form a negatively
charged [emimCO 2]−. However, this complex may be
reprotonated to form the overall neutral molecule shown in
eq 1. The proton removed from the C2 position is not seen in
the 1H NMR of the solution after electrolysis (c) or in the
precipitate (d); i.e., there is no 2′ in either spectrum. However,
if the H+ is attached to the complex, we would anticipate fast
exchange of that proton between the carboxylate site and the
polar solvent, so that it would not show up in the 1H NMR.27,30
[emim] + CO2 + H+ + e− → ([emimCO2 ]− ···H+) (1)
Figure 5 shows the products formed and the Faradaic
efficiency as a function of time for electrolysis of CO2-saturated
0.1 M TEAP/AcN solution (A and B) and CO2-saturated 0.1
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Figure 5. Formation of the products (a) oxalate anion, (b) CO, and (c) carboxylate anion during the course of electrolysis and the corresponding
Faradaic efficiency using two different electrolytes: (A and B) 0.1 M TEAP/AcN (applied potential of −2.40 V vs Ag/AgNO3) and (C and D) 0.1 M
[emim][Tf2N]/AcN (applied potential of −2.25 V vs Ag/Ag NO3). The electrolyte was kept saturated with CO2. The Faradaic efficiency was
monitored from the charges flowed during the reduction period.

Figure 6. Effect of [emim][Tf2N] concentration on the distribution of CO2 reduction products: (A) (a) oxalate and (b) CO, and (B) (b) CO and
(c) carboxylate. The electrolysis was carried out at −2.34 V (vs Ag/AgNO3) in CO2-saturated AcN containing 0.1 M TEAP and varying
concentrations of [emim][Tf2N]. The products were analyzed after 1 h of electrolysis.

M [emim][Tf2N]/AcN solution (C and D). In agreement with
previous studies, the product of electrochemical reduction of
CO2 in nonaqueous media using Pb as the working electrode
and TEAP as the supporting electrolyte is predominantly
oxalate anion.12,22−24,31 When we used 0.1 M [emim][Tf2N]/
AcN as the supporting electrolyte, CO and an imidazolium−
carboxylate species become the prominent products. In the 0.1
M [emim][Tf2N]/AcN system, the Faradaic efficiency of the
imidazolium carboxylate decreased with time and that of CO
increased with time, until equilibrium values were reached after
an hour or two.
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Obviously, the presence of [emim][Tf2N] changes the
course of the CO2 reduction reaction so that it produces CO
and an imidazolium−carboxylate complex and suppresses the
dimerization of CO2−• to form oxalate. We further explored the
role of [emim][Tf2N] in switching the course of the reaction by
varying its concentration in a 0.1 M TEAP/AcN solution and
monitoring the product distribution of CO2 electrochemical
reduction.
2.3. Shifting the Course of the Electrochemical
Reduction of CO2 with [emim][Tf2N]. Cyclic voltammo-
grams were recorded using a Pb working electrode (Supporting
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Scheme 1. Reaction Pathways for the Electrochemical Reduction of CO2 in the (A) Absence and (B, C) Presence of
[emim][Tf2N] at a Pb Electrode in AcN
Information, Figure S8) in N2- and CO2-saturated 0.1 M
TEAP/AcN solutions with different concentrations of [emim]-
[Tf2N]. We applied a constant potential of −2.34 V (vs Ag/
AgNO3) to carry out CO2 electrolysis for a period of 1 h. The
concentration of products and current that flowed through the
circuit were monitored to estimate the Faradaic efficiency. As
shown in Figure 6A, CO increases and oxalate anion decreases
with increasing concentration of the IL [emim][Tf2N]. Another
reduction product is imidazolium carboxylate, which is formed
in significant amounts during the electrolysis (Figure 6B).
It is evident from the product analysis that [emim][Tf2N]
can switch the course of the electrochemical reduction reaction,
leading to the formation of CO and suppressing the oxalate
anion formation. It has been reported that CO is produced in
the electrochemical reduction of CO2 in nonaqueous media at
metal working electrodes, such as In, Zn, Sn, Au, Hg, Pb, and
Pt, followed by the disproportionation of CO2−• (reaction
2).22,23,31−33 On the other hand, in aqueous media protons can
interact with CO2−• to produce CO (reaction 3).1,7,10,11,23,34
2CO2−• → CO + CO32 − (2)
CO2−• + 2H+ → CO + H 2O (3)
We further probed the involvement of reactions 2 and 3 in
our experiments. The 13C NMR spectrum of the electrolysis
sample (Supporting Information, Figure S6) did not show any
carbonate species, which would have to be produced in an
amount equal to the amount of CO formed if reaction 2 were
taking place. This rules out the disproportionation of CO2−•
(reaction 2) in the electrolysis of CO2-saturated 0.1 M TEAP/
AcN plus [emim][Tf2N] mixtures. We also explored the
possibility of CO being formed by reaction of CO2−• with H+
ions (reaction 3) by adjusting the proton ion concentration
through addition of sulfuric acid or tetraethylammonium
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hydroxide. This produced no change in the amount of CO
produced, thus eliminating reaction 3 as the mechanism.
Gu et al. reported a mechanism where N-heterocyclic
carbenes (NHC) catalyzed CO2 splitting to form CO when
aromatic aldehydes were used as oxygen acceptors. They
proposed a reaction scheme where CO2 reacted with the NHC,
resulting in the formation of an imidazolium carboxylate, which
subsequently reacted with added aromatic aldehyde to generate
an intermediate species that was likely stabilized by
intermolecular hydrogen bonding. The H+ on the imidazolium
ring of the intermediate species was trapped by the added base,
leading to the splitting of CO2 and formation of the
corresponding aromatic salt. Finally, CO was released from
the NHC−CO complex, which regenerated the NHC, which
could proceed to the next catalytic cycle.8 The detection of a 1-
ethyl-3-methylimidazolium-2-carboxylate complex in our ex-
periments and the leveling off of the Faradaic efficiency of both
the carboxylate and CO as a function of electrolysis time
suggest that CO could be generated from the imidazolium
carboxylate in our system, as well. To test this hypothesis, we
used trimethylimidazolium bis(trifluoromethylsulfonyl)imide
([mmmim][Tf2N]) as the supporting electrolyte. In this IL
the proton at the C2 position is replaced with a methyl group,
making the formation of a carbene impossible. To our surprise,
CO was produced with an Faradaic efficiency of 57.2% for 1 h
electrolysis at −2.25 V (vs Ag/Ag NO3), even higher than that
of 39.2% with [emim][Tf2N] as the electrolyte, which suggests
that CO does not originate from the 1-ethyl-3-methylimidazo-
lium-2-carboxylate; rather, the carboxylate may be a competing
species formed concomitantly with CO.
Finally, our observation that CO is formed preferentially over
oxalate when [emim][Tf2N] is added to TEAP/AcN is similar
to what occurs with the addition of a surfactant.35 This
indicates that ILs ([emim][Tf2N] and [mmmim][Tf2N]) may
play a role similar to that of surfactants, thus helping to stabilize
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CO2−•, which is responsible for the reduced overpotential for
the CO2 reduction reaction. Moreover, the presence of ILs
modifies the course of the electrochemical reduction of CO2 in
nonaqueous solution. Analogous to Rosen et al.’s study,10 the
formation of CO in our system can be attributed to the
interaction between CO2 and the cation of the IL at the
electrode surface. When only TEAP is used as the supporting
electrolyte, CO2−• dimerizes on the surface of the Pb electrode
to yield oxalate (shown in Scheme 1A). When an imidazolium
IL is added, the cathode surface becomes covered with both
CO2−• and the cations of the IL. The imidazolium cation
stabilizes the CO2−•, prevents close approach of two CO2−•,
and inhibits dimerization to form oxalate (Scheme 1B). In
addition, CO2−• reacts with the [emim]+ cation to form
carboxylate (Scheme 1C). Therefore, when [emim][Tf2N] is
added, two competing pathways replace dimerization of CO2−•
to form oxalate (Scheme 1A), with one leading to the
formation of CO (Scheme 1B) and the other to the formation
of the carboxylate (Scheme 1C).
3. CONCLUSIONS
The electrochemical reduction of CO2 at a Pb electrode in the
presence of ionic liquid [emim][Tf2N] shows the catalytic role
of ionic liquid in shifting the course of the reduction pathway.
The cyclic voltammograms confirm that imidazolium IL lowers
the overpotential for CO2 reduction by about 0.18 V. Most
importantly, our study shows that the course of the
electrochemical reduction of CO2 can be altered dramatically
by the presence of [emim][Tf2N]. Specifically, increasing the
concentration of [emim][Tf2N] in 0.1 M TEAP/AcN switches
the product from oxalate, the widely reported principle product
of CO2 reduction on Pb in AcN, to CO and an imidazolium
carboxylate complex. The results discussed in this investigation
further ascertain the role of imidazolium-based ionic liquid as
homogeneous catalyst for lowering the CO2 reduction potential
as well as modulating the course of the reaction.
4. EXPERIMENTAL SECTION
4.1. Materials. Acetonitrile (AcN, Fisher Scientific, 99.9%),
sodium oxalate powder (Na2C2O4, Alfa Aesar, A.C.S, 99.5+%),
potassium phosphate monobasic (KH2PO4, Fisher Scientific, A.C.S,
99.9%), and dimethyl sulfoxide (DMSO, D, Cambridge Isotope
Laboratories, 99.9%, +1% v/v TMS,) were used as purchased.
Tetraethylammonium perchlorate (TEAP) (Alfa Aeser, 98%) was
desiccated at 40 °C overnight in a vacuum oven before use.
[emim][Tf2N] and [mmmim][Tf2N] were synthesized by standard
techniques. N2 and CO2 were supplied from Airgas (purity 99.995%).
The Nafion 117 membrane (manufactured by PuPont Fuel Cells) was
treated as described in the literature before use:36,37 boiling in 3%
H2O2 aqueous solution, deionized water, 0.5 M H2SO4 aqueous
solution, and finally deionized water, successively, for 1 h for each step.
4.2. Electrochemical Measurements. Cyclic voltammetry and
chronocoulometry were performed in a two-compartment, three-
electrode glass cell. Figure S1a,b (Supporting Information) shows the
construction of the cell. The working electrode was a lead sheet (Alfa,
Aesar, 99.998%), which was polished with sand paper with a grit
designation of 320, followed by rinsing with AcN before use to remove
any oxide impurities on the surface. A geometrical surface area of 2.0
cm2 of the lead working electrode was maintained in the solution in all
electrochemical experiments. The Ag/AgNO3 electrode, made of a
silver wire immersed in 0.01 M silver nitrate dissolved in 0.1 M TEAP/
AcN, was used as the reference electrode. The reference electrode was
calibrated against a ferrocene/ferrocenium (Fc+/Fc) redox couple to
make sure it gave the right potential in reference to SHE.38 Figure S2
(Supporting Information) shows the calibration curves. The counter
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electrode was manufactured from a 25 × 25 mm platinum gauze (Alfa,
Aesar, 99.9%, 52 mesh). The working electrode and the reference
electrode were immersed in 10 mL of electrolyte solution in the
cathodic compartment of the cell, and the counter electrode was
immersed in 5 mL of electrolyte solution in the anodic compartment.
The applied potential between the reference and working electrodes
was maintained by a Gamry potentiostat. Before each set of bulk
electrolysis experiments, the cathodic compartment was purged with
N2 for 30 min to remove any moisture and dissolved oxygen, followed
by purging with CO2 for 30 min to saturate the electrolyte. Cyclic
voltammograms of the Pb electrode in N2- and CO2-saturated
electrolyte were taken between −1.50 and −2.50 V (vs Ag/Ag NO3) at
a sweep rate of 50 mV/s right after purging the gas. Generally, the
surface of the working electrode was electrochemically conditioned,
and equilibrium was reached after 10 CV cycles with the electrolyte
kept under the N2 or CO2 atmosphere. The data reported corresponds
to the last cycle. Chronocoulometry was carried out in the closed cell
with an applied potential of −2.40 and −2.25 V for 0.1 M TEAP/AcN
and 0.1 M [emim][Tf2N]/AcN, respectively.
4.3. Product Characterization. Fourier transform infrared
spectroscopy (FTIR) (Bruker Tensor 27) was used for the IR
measurements of the precipitate generated from CO2 reduction with
TEAP as the electrolyte. Sodium oxalate powder was used as a
standard. The precipitate was separated and purified from the
electrolysis solution in a centrifuge at 6000 rpm for 15 min, followed
by rinsing with pure AcN. The separation and purification were
repeated three times. Figure S3 (Supporting Information) shows the
IR spectra of the blank, standard, and unknown samples.
The NMR measurements were performed on a Varian spectrometer
operating at 600 MHz Larmor frequency. The samples were dissolved
in DMSO, wherein the electrolysis solution was dried on a rotary
evaporator at 40 °C under vacuum. The precipitate generated in
[emim][Tf2N]/AcN was separated and purified similarly.
High-performance liquid chromatography (HPLC) was performed
on an Alliance-Waters HPLC instrument with a C18 reversed phase
(RP) column (250 × 4.6 mm i.d., OOG-4299-E0, Phenomenex). The
mobile phase was AcN/10 mM KH2PO4 aqueous solution of pH 2.5
(5:95) at a flow rate of 0.5 mL/min. A standard calibration curve was
developed to determine the concentration of oxalate generated in the
unknown samples (Supporting Information, Figure S4).
The gaseous product of CO2 reduction was analyzed with a gas
chromatography (GC) instrument (Thermo Scientific) equipped with
a thermal conductivity detector (TCD). A molecular sieve 5A column
was used with helium as the carrier gas at a constant pressure of 3 psi.
The temperature of the oven was set at 65 °C for 4.5 min. The
standard calibration curve developed to quantify CO in unknown
samples is shown in Figure S5 (Supporting Information).
■
ASSOCIATED CONTENT
*
S Supporting Information
Construction of the electrochemical cell, IR spectra, and
calibration curves are presented. This material is available free
of charge via the Internet at http://pubs.acs.org/.
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: jfb@nd.edu (J.F.B.), pkamat@nd.edu (P.V.K.).
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
The authors acknowledge the Notre Dame Sustainable Energy
Initiative for financial support during this project. We also
thank the Notre Dame Center for Environmental Science and
Technology (CEST) for free access to the facilities.
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■
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dx.doi.org/10.1021/la5009076 | Langmuir 2014, 30, 6302−6308