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Accepted Article

Title: Catholyte-Free Electrocatalytic CO₂ Reduction into Formate

Authors: Wonhee Lee, Young Eun Kim, Min Hye Youn, Soon Kwan
Jeong, and Ki Tae Park

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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201803501

Angew. Chem. 10.1002/ange.201803501

Link to VoR: http://dx.doi.org/10.1002/anie.201803501

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Angewandte Chemie International Edition 10.1002/anie.201803501

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Catholyte-Free Electrocatalytic CO2 Reduction into Formate

Wonhee Lee, Young Eun Kim, Min Hye Youn, Soon Kwan Jeong, and Ki Tae Park*
Abstract: Electrochemical reduction of carbon dioxide (CO2) into
value-added chemicals is a promising strategy to reduce CO2
emission and mitigate climate change. One of the most serious
problems in electrocatalytic CO2 reduction (CO2R) is the low
solubility of CO2 in an aqueous electrolyte, which significantly limits
the cathodic reaction rate. This paper proposes a facile method of
catholyte-free electrocatalytic CO2 reduction to avoid the solubility
their method still suffered from a high cell voltage of 3.7 V, a low
FE of 70 %, and the need for product separation from the
catholyte. A catholyte is not the only medium that provides
dissolved CO2 as a cathode reactant but also serves as a passage
to transfer electrons and ions. However, the use of catholytes
causes a solubility problem, and it has to be removed, especially
in order to recover liquid products, such as formic acid or formate

Accepted Manuscript
limitation using commercial tin nanoparticles as a cathode catalyst. solution. Even though some researchers have investigated a
Interestingly, as the reaction temperature rises from 303 K to 363 K, direct electroreduction of gaseous CO2 to circumvent the solubility
the partial current density (PCD) of formate improves more than two limitation, the FE towards formic acid was only 5% and the partial
times with 52.9 mA cm-2, despite the decrease in CO2 solubility. In current density (PCD) of formate was very poor (< 0.5 mA cm-
2 [16,20]
addition, a significantly high formate concentration of 41.5 g L-1 is ).
obtained as a one-path product at 343 K with high PCD (51.7 mA Here, we report a facile strategy of catholyte-free
cm-2) and high Faradaic efficiency (93.3%) via continuous operation electrocatalytic CO2 reduction (CF-CO2R) that avoids the
in a full flow cell at a low cell voltage of 2.2 V. solubility limitation by supplying an appropriate amount of water
vapor with gaseous CO2 as a cathode reactant. Gaseous CO2 at
a flowrate of 300 mL min-1 was supplied to the cathode channel of
The electrocatalytic CO2 reduction (CO2R) into useful
a 25 cm2 full flow cell (Figure S1) through a bubble humidifier set
chemicals or fuels has attracted significant interest for renewable
to a specific temperature to control the amount of vapor supply
energy storage and environmental sustainability. [1–4] There are
(Figure S2). The water vapor acts as a carrier for supplying
several electrochemical pathways to convert CO 2 into valuable
dissolved CO2 to the catalyst surface by forming a CO2-saturated
products [1,5,6], among which formic acid or formate has received
thin liquid film on the catalyst surface, and CO2 consumed by the
particular attention over the past few years because the CO2R
reaction in the film is immediately replenished from the bulk gas
into formic acid is regarded as a suitable reaction for industrial
stream (Scheme 1). This method improves the mass transfer of
scale production.[7–9] However, there still remain some problems
CO2, resulting in a high PCD and a high FE even at a low cell
to be solved, including a large overpotential, low Faradaic
voltage. In addition, a significantly high formate concentration can
efficiency (FE), and poor stability of electrocatalysts. In particular,
be achieved by the CF-CO2R by providing dissolved CO 2
the low solubility of CO2 in the catholyte significantly limits the
sufficiently with extremely small amount of water. We
reaction rate, thus greatly hindering the large-scale application
demonstrated an excellent electrolytic performance of CF-CO2R
of the CO2R.[1] Furthermore, the liquid electrolytes dilute the
into formate using commercial tin (Sn) nanoparticles as the
reduction products, which increases the separation costs for
cathode catalyst by increasing the reaction temperature and by
product recovery.
varying the vapor supply. In the CF-CO2R system, a typical
Some efforts have been reported to overcome the solubility
anolyte, 1 M KOH solution, was used same as the conventional
limitation and enhance the current density of formate production,
CO2R. For comparison, the conventional CO2R (Figure S3) was
including development of a highly porous structure of SnO2,
also examined using a CO2-saturated aqueous solution of 1 M
tunable alloys, and Ionic liquids (ILs).[2,10–13] Despite these
KCl as a catholyte (see also Figure S4). Additionally, the long-
significant results, their kinetics of CO2R into formate is still limited
term stability of the CF-CO2R system was also demonstrated (see
by the low CO2 concentration in electrolytes. In recent years,
Supporting Information (SI) for details).
some research groups reported remarkable improvement in the
current density of CO2R to formate using gas diffusion electrodes
(GDEs) with metal nanoparticles.[5,14–19] This type of electrode
provides a three-phase interface of gas / electrolyte / catalyst, in
which the CO2 molecules only have to diffuse through a very thin
liquid layer of electrolyte in order to reach the catalyst surface. [19]
Castillo et al.[5] achieved a high formate concentration of 2.5 g L-1
via continuous operation of a 10 cm2 filter-press cell using Sn-
GDEs under galvanostatic condition of 150 mA cm-2. Although
they obtained an enhanced performance over previous results,

[*] Dr. W. Lee, Dr. Y. E. Kim, Dr. M. H. Youn, Dr. S. K. Joeng, Dr. K. T.
Park
Greenhouse Gas Laboratory, Korea Institute of Energy Research,
Daejeon 34129, Korea
E-mail: ktpark@kier.re.kr
Scheme 1. Schematic diagram of the catholyte-free electrocatalytic CO2
Supporting information for this article is given via a link at the end of
reduction (CF-CO2R) system for formate synthesis.
the document

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Angewandte Chemie International Edition
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Figure 1. The electrolytic performances of CF-CO2R with a vapor supply of 12.58 mg min-1 cm-2 as a function of cell temperature, compared with the conventional
CO2R using a 1 M KCl catholyte at a cell voltage of 2.2 V. A) FEs of formate, B) PCDs of formate, and C) formate (HCOO-) concentrations.
Several researchers found that lower temperatures
suppressed the hydrogen evolution reaction (HER) and increased
the efficiency for CO2R because the positive effect of a
temperature increase on the intrinsic kinetics of CO 2R is
countered by a decrease in CO2 solubility (Table S1) in the
catholyte.[1,21–23] In particular, for the Sn electrode, the FE of
formate decreased with an increasing temperature above 293
K.[23,24] We examined the electrolytic performances of CF-CO2R
by increasing the reaction temperature to confirm that the
solubility constraint could be overcome at a cell voltage of 2.2 V
with a constant vapor supply of 12.58 mg min -1 cm-2. The FE for
formate in the CF-CO2R as a function of cell temperature is shown
in Figure 1A and compared with the conventional CO2R using a 1
M KCl catholyte (Figure S5). As expected, in the conventional
CO2R, the FE of formate decreased drastically from 66.7% to 22.6%
with an increasing cell temperature from 303 K to 363 K. On the
other hand, the FEs in the CF-CO2R were more than 90% up to
343 K, and 84.8% even at 363 K (Figure 1A).
Moreover, as the cell temperature rose from 303 K to 363 K,
the PCD increased more than double in the CF-CO2R (52.9 mA
cm-2 at 363 K) despite the decrease in CO2 solubility to one-
fourth[25], while the PCD in the conventional CO2R decreased
below half (10.9 mA cm-2 at 363 K) (Figure 1B). This clearly
reveals that the cathode reaction is not limited by the CO2
solubility in the CF-CO2R system, but the kinetics of CO2R
accelerates with temperature. In addition, in the CF-CO2R, the
PCD increased monotonically up to 343 K, but the slope
decreased at 363 K due to the rapidly increased amount of water
crossover (Figure S6). The volumes of product by CF-CO2R
increased along with the increase of water crossover with cell
temperature, and the water crossover rapidly increased at 363 K
due to membrane swelling. The enhanced PCDs of the CF-CO2R
resulted from the fast mass transfer rate of CO2 through the thin
liquid film; therefore, it is important to keep the water film thin. The
excess amount of water crossover from the anode at 363 K
formed a thicker water film on the catalyst surface, which
increased the mass transfer resistance.
The cell temperature also enhances the formate
concentration, because the higher temperature improves the PCD
of formate production in the CF-CO2R, except for the cell
temperature at 363 K (Figure 1C). The excessive water crossover
at 363 K not only cancels out the acceleration of kinetics by
temperature but also dilutes the concentration of formate, and
thus results in a lower formate concentration than that at 343 K.
Above all, two orders of magnitude higher concentrations of
formate were obtained from the CF-CO2R compared to those from
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10.1002/anie.201803501
Accepted Manuscript
CO2R using a 1 M KCl catholyte (Figure 1C). Before this study,
the highest formate concentration reported in the literature to date
was 16.9 g L-1 with a FE of 42.3% for formate production at a cell
voltage of 4.3 V [5], while the use of water vapor instead of
catholyte in the CF-CO2R extremely reduces the amount of water
in the product, facilitating a significantly high concentration of
formate (41.5 g L-1) as a one-path product at 343 K with a high
PCD (51.7 mA cm-2) and a high FE (93.3%) at 2.2 V. Therefore,
the CF-CO2R provides a simple process without electrolyte
separation for product recovery.
Figure 2. A) The dependences of FEs (formate, H2, and CO), PCD of formate,
and formate concentration on the amount of vapor supply, and B) the stability
of the current density with three different vapor supply conditions at a cell
voltage of 2.2 V and at a cell temperature of 323 K.
Interestingly, the formate concentration can be controlled by
the supply amount of water vapor, and the highest formate
concentration reached 116.2 g L-1 with FE of 77.7% by reducing
the vapor supply from 12.58 to 0.65 mg min-1 cm-2 at 2.2 V with a
cell temperature of 323 K as shown in Figure 2A, which also
indicates that formate, H2 and carbon monoxide (CO) are the
main products with a total FE of around 100%. The vapor supply
was determined by varying the temperature of a bubble-type
humidifier from 327 K to 365 K (Figure S7). The amount of water
vapor supply increased with the humidifier temperature, and the
experimental vapor pressures were slightly lower than the
saturated vapor pressure at a given humidifier temperature (Table
S2, Figure S8). The CF-CO2R exhibited higher FEs as the vapor
supply increased, and FEs over 90% were obtained at a vapor
supply above 3.64 mg min-1 cm-2. Although a higher formate
concentration can be produced with a lower vapor supply, a vapor
supply below an appropriate level also causes mass transfer
resistance as with excess vapor supply. This is because the
production of formate with a high concentration indicates the
Angewandte Chemie International Edition
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synthesis of a dense product (Figure S9), making it difficult for the
formate to be released from catalyst surface, and it forms a dense
liquid film on the catalyst surface, which interferes with CO2
transport. For this reason, the lowest vapor supply among the
tested conditions (0.65 mg min-1 cm-2) shows periodic unstable
current densities by the repetition of formate accumulation and
release on the catalyst surface (Figure 2B). The highest PCD
(41.5 mA cm-2) was obtained when the vapor supply was 7.52 min-
1
cm-2, which reveals that a vapor supply of 12.58 min-1 cm-2 is
excessive at a cell temperature of 323 K. The current density at a
vapor supply of 12.58 mg min-1 cm-2 was also unstable due to the
mass transfer resistance caused by excessive vapor supply
(Figure 2B). Therefore, an appropriate vapor supply is important
for FE, PCD, and the product concentration of the CF-CO2R. The
vapor supply must be determined by considering the cell
temperature, because the amount of water condensed on the
catalyst surface varies according to the cell temperature, even if
the same amount of water vapor is supplied from the humidifier.
Figure 3. The applied cell voltage dependence of A) FEs for products and
energy efficiency of CO2R into formate, and B) current density, PCD of formate
and formate concentration.
The electrolytic performances of the CF-CO2R also depend
on the cell voltage. The CF-CO2R tests at a series of applied cell
voltages from 1.9 V to 2.5 V were carried out at a cell temperature
of 343 K with a vapor supply of 12.58 mg min-1 cm-2. The
dependence of the FEs for the products on cell voltage is depicted
in Figure 3A. The selectivities toward formate and H2 exhibited a
strong dependence on the applied cell voltage, and they exhibited
an exactly opposite tendency to the cell voltage, whereas the FE
of CO occupied a small proportion and decreased from 2.3% to
0.5% with an increasing cell voltage from 1.9 V to 2.5 V. The FE
for formate production was 80.7% at an applied cell voltage of 1.9
V, and the FE of formate increased with the cell voltage to reach
the maximum value of 95.0% at 2.1 V. Additionally, the energy
efficiency of the formate production of the CF-CO2R system was
also calculated and is plotted versus cell voltages in Figure 3A as
calculated by Equation (1):[11]
(1)
Where, ∆E0 represents the difference between the standard half
reaction potentials for water oxidation (1.23 V vs. RHE) and CO2R
to formate (-0.2 V vs. RHE). The energy efficiency of the CF-CO2R
exhibited a similar tendency to the FE on the cell voltage. In
addition, the highest energy efficiency of 64.7% was obtained at
2.1 V, indicating that the CF-CO2R allowed a high FE (95.0%) at
This article is protected by copyright. All rights reserved.
10.1002/anie.201803501
a low overpotential (0.67 V), including both anodic and cathodic
overpotentials. The energy efficiency reported here is the highest
energy efficiency of CO2R to formate of all those of published
previously.
As expected, the current density of the CF-CO2R increased
with the applied cell voltage, while the kinetics of the CO2R to
formate reached a maximum at 2.4 V in the same trend as the
formate concentration on the cell voltage (Figure 3B). These
tendencies of FE and PCD on the applied cell voltage show that
there is only a narrow cell voltage range for selective formate
production with high PCD and high energy efficiency due to
competition with the HER. At a cell voltage below 2.1 V, the HER
begins to increase because it is thermodynamically and kinetically
Accepted Manuscript
favorable, and the HER also increases in the cell voltage region
above 2.2 V since CO2R is mass transfer limited.[10] In the CF-
CO2R, the PCD of formate improved up to 60.4 mA cm-2 with an
increasing applied cell voltage until 2.4 V; however, the FE was
only 76.6% and dropped to 60.2% at 2.5 V. The PCDs were 41.7
mA cm-2 and 51.8 mA cm-2, respectively, at the cell voltages of 2.1
V and 2.2 V, where the FEs were greater than 90%. Consequently,
the appropriate cell voltage region that satisfied high selectivity (>
90 %), high energy efficiency (> 60%) and fast kinetics (> 40 mA
cm-2) of the CO2R to formate was in the range from 2.1 V to 2.2 V.
Figure 4. The stability of current densities and FEs of formate in the CF-CO2R
and the CO2R using 1 M KCl during 48 h at 2.2 V.
To evaluate the stability of the CF-CO2R, electrolysis was
performed continuously during 48 h at 2.2 V and 323 K with vapor
supply of 3.64 mg min-1 cm-2. The conventional CO2R using a 1 M
KCl was also carried out for comparison during 48 h at 2.2 V and
303 K. The current density and FE of formate obtained from 48 h
of operation are shown in Figure 4 (Figure S10). The FE of
formate in the conventional CO2R decreased from 67.7% to 31.8%
after 48 h, while a high FE of 91.2% was stably maintained over
48 h in the CF-CO2R. It is considered that the stable performance
of Sn catalyst in the CF-CO2R is due to the low cell voltage (2.2
V) compared to those in literatures, where -2.0 V (vs. Ag/AgCl)
was applied only for the cathode potential and the crystal structure
of Sn catalysts were destroyed after about 40 h and 60 h
operation [26,27] (Table S3). When compare the Sn catalyst before
and after electrolysis in the CF-CO2R, there were almost no
changes in structure, surface composition, and morphology
(Figure S11-S13). However, a significant damage was observed
in the morphology of Sn catalyst layer after electrolysis using a
KCl catholyte (Figure S13), caused by the flow of catholyte and
the flow of H2 evolution due to the lower FE of formate. Therefore,
it is considered that the CF-CO2R method has advantages in
stability of CO2R by preventing electrochemical and physical
Angewandte Chemie International Edition 10.1002/anie.201803501

COMMUNICATION
damages on Sn catalyst via applying low cell potential without [18]
catholyte.
[19]
In summary, we proposed a simple strategy for the CF-
CO2R to improve the electrolytic performances of the CO2R into
[20]
formate with circumvention of the CO2 solubility limitation. The
CF-CO2R method provides a sufficient dissolved CO2 for the [21]
cathodic reaction with extremely reduced water amount, which [22]
result in a significantly improved formate concentration with high [23]
CO2R performances. Our results indicated that improved CO2R
performances and long-term stability can be achieved by the
[24]
facile method of “catholyte-free” with commercial Sn catalyst
without catalysts prepared by advanced techniques. Therefore,
[25]
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Accepted Manuscript
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Acknowledgements

This work was conducted under framework of the research and

development program of the Korea Institute of Energy Research
(B8-2431).

Keywords: CO2 reduction • electrocatalysis • catholyte-free •

electrolytes • formic acid

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Fast and efficient CO2 reduction: A Wonhee Lee, Young Eun Kim, Min Hye
facile strategy of ‘catholyte-free Youn, Soon Kwan Jeong,
electrocatalytic CO2 reduction (CF- and Ki Tae Park*
CO2R)’ for formate production is
proposed to avoid a solubility Page No. – Page No.
limitation in an aqueous electrolyte.
Catholyte-Free Electrocatalytic CO2
The CF-CO2R method provided an
Reduction into Formate
increased CO2 transfer rate to the
electrocatalyst and showed a

Accepted Manuscript
significantly high formate
concentration at a high current
density with a high Faradaic efficiency
for formate production at a low cell
voltage.

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