Chemical Engineering Journal 293 (2016) 161–170

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Chemical Engineering Journal

journal homepage: www.elsevier.com/locate/cej

Electrochemical reduction of CO2 to formate in aqueous solution using

electro-deposited Sn catalysts
Chenchen Zhao a, Jianlong Wang a,b,⇑
a
Collaborative Innovation Center for Advanced Nuclear Energy Technology, INET, Tsinghua University, Beijing 100084, PR China
b
Beijing Key Laboratory of Radioactive Wastes Treatment, Tsinghua University, Beijing 100084, PR China

h i g h l i g h t s g r a p h i c a l a b s t r a c t

Sn catalytic electrodes were prepared

using electro-deposition method.

Sn catalysts were used for CO2
electrochemical reduction.

The deposited Sn catalysts exhibited a
crystal pattern of (1 0 1) and (1 1 2)
faces.

The Faradaic efficiency of CO2
conversion was over 91% at 1.4 V vs.
SCE.

a r t i c l e i n f o a b s t r a c t

Article history: Carbon dioxide as an abundant carbon resource can be used for the production of useful chemicals
Received 6 November 2015 through electrochemical conversion. Catalyst is a key element for CO2 electrochemical reduction, which
Received in revised form 18 February 2016 determines the crucial factors in the process. In this paper, a series of Sn catalytic electrodes were pre-
Accepted 20 February 2016
pared using electro-deposition method with controlled current density at room temperature, and applied
Available online 27 February 2016
to the electrochemical reduction of CO2. The experimental results showed that the deposited Sn catalysts
exhibited a crystal pattern of the (1 0 1) and (1 1 2) faces and the thickness of deposited layer varied with
Keywords:
the deposition current density. The activity of these electrodes was determined in H-type and 3-
Electrochemical reduction
Carbon dioxide
elelctrode system, and the reduction product was quantitatively analyzed by ion chromatography. The
Sn catalyst optimized deposition current density for Sn fabrication was found to be 15 mA cm2, on which the
Formic acid Faradaic efficiency of CO2 conversion was over 91% at 1.4 V vs. SCE.
Electro-deposition Ó 2016 Elsevier B.V. All rights reserved.

1. Introduction which could be further utilized as industrial feedstock [3–7]. How-

The ever-growing global warming caused by greenhouse gas
such as CO2 has attracted extensive attention [1]. In the past sev-
eral decades, various technologies have been developed to address
this climate change issue [2]. Among them, the electrochemical or
photo-electrochemical method is promising for it can reduce CO2
to produce diverse useful chemicals, such as HCOOH, CO, CH4,
⇑ Corresponding author at: Neng Ke Lou, Tsinghua University, Beijing 100084, PR
China. Tel.: +86 10 62784843; fax: +86 10 62771150.
E-mail address: wangjl@tsinghua.edu.cn (J. Wang).
ever, the efficiency and selectivity of the catalysts are not satisfac-
tory. The efficient catalysts are very crucial for the electrochemical
conversion of CO2, which need further study to improve the cat-
alytic performance [6–9].
Different types of catalysts have been investigated, including
metal electrodes. Sn-based electrode is attractive because of its
low over-potential in aqueous medium, non-toxic property and
comparatively high selectivity towards formate or formic acid
which is a good candidate for fuel cells [9–25]. The reactivity of
Sn catalyst can be affected largely by the property of the electrode
as well as reaction conditions [26], the Faradaic efficiency varied

http://dx.doi.org/10.1016/j.cej.2016.02.084
1385-8947/Ó 2016 Elsevier B.V. All rights reserved.
162 C. Zhao, J. Wang / Chemical Engineering Journal 293 (2016) 161–170

Scheme 1. Preparation of electrodeposited Sn electrodes prepared at different current density (a) 5; (b) 10; (c) 15; and (d) 20 mA cm2.

2. Experimental

2.1. Catalyst synthesis

The Sn/Cu electrode was prepared through a facile electro-

deposition method. The deposition electrolyte was freshly
prepared from an aqueous solution of 0.1 M SnCl22H2O, using
0.4 M K4P2O73H2O as complexing agent to form more stable metal
complexes and to decrease metallic ion activity [29,30], while
0.05 M tartaric acid, 0.2 g L1 quinol, 0.1 g L1 sodium dodecyl
benzene sulfonate and 0.5 g L1 gelatin were added as additives.
Cu thin film (13 lm, 99.99%, 24 cm2) and a cuboid tin block
were used as the working electrode and sacrifice positive elec-
trode, respectively. Cu film was soaked in sulfuric acid solution,

Scheme 2. Schematic illustration of the electrochemical reduction of CO2 on

electrodeposited Sn electrodes with an H-type 3 electrode cell.

from 18% to 95%, depending on the morphology and structure of

catalyst.
There are a variety of methods to prepare Sn electrode. Lee et al.
applied the electro-deposition technology to prepare Sn/carbon-
paper gas diffusion electrode, they found that the Faradaic effi-
ciency was 18% on average [18]. However Sridhar group reported
a value of 80% using similar prepared Sn electrode [11]. The differ-
ence may result from the ingredient of the deposition bath and
experimental conditions in the process of crystal growth, which
lead to different electrode characteristic. Using K4P2O73H2O and
SnCl22H2O as plating solution to electrodeposit Sn onto the Cu
base is a widely used method to prepare a composite material
for Li-ion battery electrode [27]. However this method has seldom
been used for preparing the catalysts for CO2 reduction. By tuning
the deposition current density, we can obtain electrodes with var-
ied surface structure and morphology. In addition, placing a certain
metal catalyst over-layer on a foreign metal substrate can provide
an alternative option for tuning the selectivity [28].
The objective of this work was to investigate the electrochemi-
cal reduction of CO2 using a series of Sn catalysts electrodeposited
onto Cu film with controlled deposition current density. The two-
layer Sn/Cu electrodes were evaluated using different characteriza-
tion techniques to establish the relationship between morphology Fig. 1. XRD pattern of electrodeposited Sn electrodes prepared at different current
or structure and electrochemical catalytic activity. density (a) 5; (b) 10; (c) 15; and (d) 20 mA cm2.
 C. Zhao, J. Wang / Chemical Engineering Journal 293 (2016) 161–170 163

Fig. 2. SEM images of the surfaces and cross-sections of the four electrodes (a) 5; (b) 10; (c) 15; and (d) 20 mA cm2.

then washed with ethanol, deionized water to remove the oil and
then for removing the oxide on the surface. The deposition
experiments were carried out in a rectangular cell connected to a
potentiostat (Princeton Parstat 2273) [27]. The non-active surface
of Cu film was covered with insulation tape to make sure that only
one surface was covered with Sn.
The electro-deposition current densities were 5, 10, 15
and 20 mA cm2 and deposition time was fixed at 10 min. The pre-
pared electrodes were washed in deionized water and dried in an
oven at 60 °C. The schematic process for preparation is shown in
Scheme 1.
2.2. Characterization techniques
2.2.1. X-ray diffraction (XRD)
XRD patterns of the catalysts were acquired on a Bruker D8
Advance X-ray diffractometer with filtered Cu-Ka radiation at
40 kV and 40 mA. The crystalline phases were identified by
comparing with reference patterns in previous studies.
2.2.2. Scanning electron microscope (SEM)
The SEM images of both cross-section and surface of the cata-
lysts were observed using a HITACHI SU-8010 scanning electron
164 C. Zhao, J. Wang / Chemical Engineering Journal 293 (2016) 161–170

Table 1
The cathodic peak potential Epc and current density jpc, and current density at the end
of each LSV test jend of electrodeposited Sn electrodes.

Deposition current Atmosphere Epc jpc jend

for Sn synthesis (V vs. RHE) (mA cm2) (mA cm2)
(mA cm2)
5 N2 0.096 0.460 3.189
CO2 0.155 0.285 6.158
10 N2 0.126 0.212 2.383
CO2 0.083 0.111 16.285
15 N2 0.064 0.511 4.875
CO2 0.062 0.188 8.033
20 N2 0.057 1.165 41.297
CO2 0.116 0.892 32.851
Cu film N2 – – 3.745
CO2 – – 4.393

Fig. 3. Variations in the amount of Sn deposition and thickness of Sn layer with

electro-deposition current density (a) 5; (b) 10; (c) 15; and (d) 20 mA cm2.
microscope with extra high tension at 10 kV. Sn/Cu samples were
loaded on a copper sample stage without any pretreatment.
2.3. Electrochemical reduction of CO2
The electrochemical reduction of CO2 was conducted using an
H-type, 3-electrode cell, using the as-prepared Sn/Cu tissue as
the working electrode, Saturated Calomel Reference Electrode
(SCE, TianjinAida Co. Ltd) as reference electrode and platinum wire
(TianjinAida Co. Ltd) as the counter electrode, respectively. The
three electrodes were immersed in aqueous solution of 0.1 M
KHCO3 as the electrolytes. To avoid formic acid oxidation by Pt
counter electrode, a Nafion 211 Proton Exchange Membrane
(DuPont) was adopted to separate cathode and anode area. A lug-
gin capillary was used to reduce the surface contact potential and
solution resistance. The electrochemical measurements were
carried out under control of a CHI630E electrochemical worksta-
tion (CH Instruments). Either N2 or CO2 was constantly bubbled
into the electrolyte to maintain CO2-free or CO2 saturated environ-
ment. The schematic process for the CO2 electrochemical reduction
is shown in Scheme 2.
The reduction products were collected at certain intervals. The
amount of generated HCOOH was determined using an ion
chromatography (ICS 2100, DIONEX) equipped with Potassium
Hydroxide Eluent Generator Cartridge, IonPac AS19 Analytical
Column (4 * 250 mm) and AG19 Guard Column (4 * 50 mm).
The relative Faradaic selectivity was determined by calculating
the charge used for HCOOH formation divided by the total charge
passed through the system, as shown in Eq. (1):
nHCOOH zF
f ¼ : ð1Þ
Q
where nHCOOH (mol) is the amount of produced HCOOH; z is the
number of electrons needed to form HCOOH from CO2, whose value
is 2 in this work; F is Faraday’s constant whose value is
96485 C mol1, and Q is total charge during the experiment [22].
3. Results and discussion
3.1. Physicochemical characterization of the electrodes
As shown in Scheme 1, the surface morphology of the electrodes
was observed. The results showed that for 5 mA cm2 sample, the
surface exhibited a dark color on the surface; while for 10 and
15 mA cm2 samples they had typical silver-white Sn deposition
layer; as for 20 mA cm2 electrode, owing to the excessive current
density, obvious gas evolution was observed during the deposition
and thus leading to the comparatively rougher and darker surface.
Fig. 1 presents the XRD patterns of four prepared electrodes. For
5 mA cm2 sample, the diffraction peaks of Cu tissue (the (2 0 0),
(2 2 0) and (1 1 1) peaks of face-centered cubic Cu) were observed
as well as the deposited Sn layer (the (1 0 1), (2 1 1) and (1 1 2) faces
of body-centered tetragonal Sn). With increase of deposition cur-
rent density, the amount of deposited Sn increased significantly
and gradually covered Cu base layer. For 15 and 20 mA cm2 sam-
ples, only a small peak of Cu (2 2 0) could be observed owing to the
effect of screw dislocations during two dimensional nucleation of
Sn growth. It was noted that a small peak of (1 0 1) CuSn alloy
was observed in 5 and 10 mA cm2 samples, suggesting that Cu
and Sn atoms on the interface migrated towards each other during
the deposition, thus generating a new phase. For 5 and 10 cm cm2
samples, the peak intensity of Sn layers was not strong enough to
cover Cu and CuSn phase, while in 15 and 20 mA cm2 samples the
good crystallinity of Sn atoms resulted in uniform Sn peaks.
The microstructure and thickness of Sn electrode played impor-
tant roles in conversion of CO2 [19,31]. Fig. 2 shows the SEM
images of the surfaces and cross-sections of four prepared
electrodes. The thickness of deposited Sn layer was measured
directly on the cross section images. For the sake of accuracy, each
thickness was measure three times in different region and the
average value was adopted as final data. For 5 mA cm2 deposited
sample (Fig. 2a), the size of deposited Sn particles was measured to
be 20–100 nm. However, obvious Sn layer could not be observed
on cross section, indicating an incomplete coverage over copper
backing foil, which was consistent with XRD patterns in Fig. 1.
For 10 and 15 mA cm2 deposited samples (Fig. 2b and c), the grain
size grew to be 0.7–1.1 lm, and the thickness of Sn layer increased
with increase of deposition current density. All three samples
exhibited a close packing among Sn particles. However, for
20 mA cm2 sample, Sn particles grew to large columns with diam-
eter of about 3 lm with loose pack, and the thickness of Sn layer
was measured to be 22.9 lm.
Differences in morphology and Sn layer thickness among these
samples could be attributed to the synergistic effect between driv-
ing forces of crystal growth and kinetic of crystal nucleating origi-
nated from deposition current. During electro-deposition, the
probability of nuclei generation w could be determined by Eq. (2)
[32]:
 
k2
w ¼ k1 exp  2 ð2Þ
g
where k1 and k2 are constant values and g is the over-potential of
working electrode. Relationship between the critical radius of gen-
erated nuclei rc and over-potential g is reported to be Eq. (3) [32]:
 C. Zhao, J. Wang / Chemical Engineering Journal 293 (2016) 161–170 165

Fig. 4. LSVs of Sn electrodes in 0.1 M KCHO3 (v = 10 mV s1). Black curves: N2-saturated solution. Red curves: CO2-saturated solution. (a) 5; (b) 10; (c) 15; and (d)
20 mA cm2; (e) Cu film as blank sample. (f) Comparison of the five LSVs. (For interpretation of the references to color in this figure legend, the reader is referred to the web
version of this article.)

ph3 E ln i ¼ A  Bg1 ð4Þ

rc ¼
6Zeg
In this equation, E is the interfacial energy; Z is the number of
electrons carried by discharge ions; e refers to the electron charge;
while h is the height of atoms on the electrode surface.
When nuclei are formed on the surface, the current density i
and over-potential g correlates as Eq. (4):
ð3Þ
Both A and B are constant values [32,33].
From Eqs. (2) to (4), we can conclude that the increase in depo-
sition current density could result in an increase in over-potential
of electrode, thus creating smaller and more compact deposits on
the electrode. However, tin is a metal of good ductility [34],
tending to form large clusters under high current density. For
166 C. Zhao, J. Wang / Chemical Engineering Journal 293 (2016) 161–170
Fig. 5. CO2 reduction electrolysis at constant potential for 1 h on different electrodes (a) 5; (b) 10; (c) 15; and (d) 20 mA cm2.
5 mA cm2 sample, the deposition current density was too low to
achieve enough Sn grains to cover the Cu base film completely,
while the coarse Sn grains were formed under low current, both
resulting in the observed dark surface. For 10 and 15 mA cm2,
they were appropriate for the deposition, creating fine and tightly
compacted structure. However, 20 mA cm2 was so high that
hydrogen evolution reaction took place, resulting in loose surface
structure and long tin columns, as well as deep color appearance
of electrode.
The deposited amount of Sn was determined by weighing the
electrode before and after electro-deposition. An approximate
linear relationship between the amount of Sn and the electro-
deposition current density was discovered (Fig. 3). The thickness
did not increase linearly with current density.
3.2. Electrochemical measurements
To examine the reduction of dissolved carbon dioxide in the
electrolyte solution, linear scanning voltammogram (LSV) technol-
ogy was employed in a typical 3-electrode system. To exclude the
formic acid oxidation on the commercial Pt wire counter electrode,
H type cell was adopted. All electrodes, including pure Cu film as
blank sample, were investigated. The scanning direction was from
0.5 V to 1.8 V vs. SCE with sweeping rate of 10 mV s1, and
0.1 M KHCO3 solution was saturated with N2 and CO2, respectively.
The pH value of N2 and CO2 saturated 0.1 M KHCO3 was mea-
sured to be 8.8 and 6.8, respectively. As pH value of the electrolyte
could influence electrode potentials for H2 and CO2 reduction, the
LSV data should be replotted to RHE as reference scale using E
(RHE) = E(vs. SCE) + 0.242 V + 0.0591 V⁄pH [22]. Both type of LSV
curves were depicted in Fig. 4. The cathodic peak Epc, cathodic
current density jpc, as well as current density at the end of each
LSV test jend are summarized in Table 1.
Generally, in N2-saturated electrolyte only reduction of HCO 3
and H2O occurs, while under CO2 saturated environment both
HCO 3 and CO2 take part in reduction of CO2, and hydrogen
evolution reaction (HER) takes place as a competing process at
metal electrode [35,36]. As reported previously [37], Sn electrode
had a thin native oxide layer on surface. A cathode peak from
0.02 V to 0.1 V vs. RHE was attributed to the reduction of tin
oxide during electrolysis [38], which could be observed in all
deposited Sn electrodes (Fig. 4a–d), but did not appear in Cu blank
sample (Fig. 4e). After replotting, this peak almost overlapped in
both N2 and CO2 saturated electrolyte at 15 mA cm2 electrode
[38], while a difference of about 40–60 mV was observed for the
other 3 samples. In most cases, the current density exhibited a
comparatively faster increase in current value after 0.05 V vs.
RHE. Fig. 4f compared five electrolysis curves of CO2 reduction. In
general, current value increased with increase of Sn amount,
except 15 mA cm2 deposited sample.
The chronoamperometry experiments were applied to examine
the stability of the electrodes in 3600 s. Moreover, HCOOH pro-
duced in solution was collected and analyzed. Given E0 = 0.67 V
vs. SCE for CO2/HCOO couple [21,39], electrolysis was performed
 C. Zhao, J. Wang / Chemical Engineering Journal 293 (2016) 161–170
Fig. 6. Variations in the faradaic efficiency, concentration of generated HCOOH and total charge passed through tin electrode with electrolysis potential. (a) 5; (b) 10; (c) 15;
and (d) 20 mA cm2.
potentiostatically at potentials between 0.6 V and 1.8 V vs. SCE
at 0.2 V intervals. CO2 was bubbled throughout the reaction pro-
cess to ensure adequate supply of feedstock. The resultant reduc-
tion current profiles were shown in Fig. 5. The current density
during electrolysis remained steady and no obvious degradation
was observed for all four samples.
4. Productivity of HCOOH
As mentioned above, electrochemical conversion of CO2 was
performed in H-cell from 0.6 V to 1.8 V vs. SCE at 0.2 V inter-
vals. In this work, no HCOOH was detected within the tested
potential range on Cu substrate, because formic acid only forms
at high over-potential [40,41]. Moreover, no formic acid was
detected at 0.6 V for all electrodes due to low applied potential.
In Fig. 6 we summarized the Faradaic efficiency, generated amount
of HCOOH and total charge per unit area during electrolysis at dif-
ferent potential of each Sn electrode.
For all electrodes, the generated amount of HCOOH displayed a
strong but not linear dependence on the applied potential. It can be
seen that as cathode potential decreased from 0.8 V to 1.8 V,
more formic acid was produced, while total charge passing through
electrode increased too, and reached maximum at 1.8 V. As illus-
trated in Eq. (1), the Faradaic efficiency was proportional to the
amount of HCOOH and inversely proportional to charge, resulting
in different dependence to applied potential. The 5 mA cm2
deposited sample was only one that the efficiency increased with
increase of over-potential, rising from 8.6% (at 0.8 V) to 64.8%
(at 1.8 V). For 10 mA cm2 sample, the Faradaic efficiency
increased with potential until 1.2 V but dropped after that, and
then rose again while going to more cathodic potentials. The sim-
167
ilar trend was observed on 20 mA cm2 sample. For 15 mA cm2
deposited sample, the curve for Faradaic efficiency exhibited a
mountain-like shape and the highest value was obtained at
1.4 V (91.7%), which was also the highest Faradaic efficiency
observed during whole work.
It has been reported previously that possible pathway for CO2
reduction on Sn-based catalyst was mainly related to a chemical
rate-determining step, as illustrated in Eqs. (5)–(9) [10,21].
CO2 ðsolutionÞ ! CO2 ðadsÞ ð5Þ
CO2 ðadsÞ þ e ! CO
2 ðadsÞ ð6Þ
CO    2
2 ðadsÞ þ HCO3 þ e ! HCO2 ðadsÞ þ CO3 ð7Þ
HCO2 ðadsÞ ! HCO2 ðsolutionÞ ð8Þ

CO2
3 þ CO2 þ H2 O ! 2HCO3 ð9Þ
To investigate the possible mechanical pathways of CO2 reduc-
tion with Sn deposited electrodes, Tafel plot of over-potential vs.
log of partial current density for HCOOH formation was depicted
using the data described above (Fig. 7). As shown in Fig. 7, for 5,
10, 15, 20 mA cm2 deposited electrodes, the slope was 169, 145,
131 and 171 mV dec1 at low over-potential region, respectively.
The slope for 10 and 15 mA cm2 samples were close to values that
were previously reported (120 mV dec1 for Sn catalysts) [42], sug-
gesting that rate-determining step (RDS) was initial electron trans-
fer to CO2 to form a surface-adsorbed CO 2 intermediate [38]. It
was speculated that the larger slope of 5 and 20 mA cm2 elec-
trodes was due to the exposed Cu substrate and loose packing
among large Sn columns, respectively.
168 C. Zhao, J. Wang / Chemical Engineering Journal 293 (2016) 161–170

Fig. 7. HCOOH partial current density Tafel plots for different electrodes. (a) 5; (b) 10; (c) 15; and (d) 20 mA cm2.

Table 2
Faradaic efficiency and Tafel slopes of HCOOH formation by CO2 reduction on
electrodeposited Sn electrodes.

Faradaic efficiency (%)

Deposition current for Sn 5 10 15 20
synthesis (mA cm2)
Potential (V vs. SCE) 0.8 8.6 6.7 4.4 6.7
1.0 9.3 36.4 13.5 9.3
1.2 18.0 68.7 24.3 71.1
1.4 34.3 51.9 91.7 4.9
1.6 59.6 43.6 77.3 26.0
1.8 64.8 58.3 57.6 43.7
Tafel slope (mV dec1) 169 145 131 171

The complete date of Faradaic efficiency and the Tafel slope

were summarized in Table 2.
From the point of practical application, sustainable stability is
important as well as a high catalytic activity. Based on the results
in Figs. 6 and 7, the stability of 15 mA cm2 Sn deposited electrode
was tested. The electrolysis was conducted at 1.4 V vs. SCE
through sequentially programmed short- and long-term
operations: six reactions for 5 min, followed by four reactions for
30 min, and continuous 3 h electrolysis. The results were shown
in Fig. 8.
During the electrolysis, current density was about
0.9–1.4 mA cm2 for first 5 min reaction, and Faradaic efficiency
was 91.0%. The other 5 short-term reactions exhibited the similar
trend, and the highest efficiency (96.6%) appeared at second
5 min reaction. Both current density and Faradaic efficiency
remained stable during first hour. However, when it came to
Fig. 8. Stability of the 15 mA cm2 deposited electrode at 1.4 V vs. SCE in a
CO2-bubbled 0.1 M KHCO3 electrolyte.
second hour, the reaction current exhibited a slow but continuous
decrease, and Faradaic efficiency dropped to about 81.6%. Both
current density and Faradaic efficiency continued to decrease as
electrolysis went on. When experiments finished, current density
decreased to 0.7 mA cm2 and the efficiency was 69.6%. The possi-
ble reason for the degradation of tin electrode may be the formation
of alkali metal intermetallic during long period electrolysis [43].
The studies on electrochemical conversion of CO2 to formic acid
on Sn-based catalyst were summarized and compared in Table 3.
 C. Zhao, J. Wang / Chemical Engineering Journal 293 (2016) 161–170
Table 3
Comparison of CO2 electrochemical conversion to formate/formic acid with Sn-based catalyst.
Electrode Experiment parameters (electrolyte, conditions)
Mixture of purchased SnO2 and Sn nanopowder CO2 dissolved NaOH solutions at different pH level
Commercial Sn 0.1 M KHCO3
5 nm tin-oxide nanoparticles 0.1 M NaHCO3
Purchased pure Sn rod 2 M KCl
1–2 lm commercial Sn sprayed onto a purchased GDL 0.5 M KHCO3
Sn powder bonded with Nafion ionomer to a purchased GDL 0.5 M NaHCO3
100 nm Sn particles annealed in air 0.1 M KHCO3, in a full electrochemical cell
Tin/tin oxide electrodes 0.5 M NaHCO3
Electrodeposited tin nanoparticles on carbon paper The CO2 gas was super-saturated with water vapor,
in a zero gap cell
Pure Sn and three modified catalysts A gas–liquid-solid half-cell
Tinned-copper 60# mesh 0.5 M KHCO3 + 0.5 M KCl, under a gas of 100% CO2
at 120 kPa(abs)
A hierarchical tin dendrite electrode 0.1 M KHCO3
Electro-deposited Sn powder 0.5 M KHCO3, 2-electrode cell
Sn GDE with addition of PTFE 0.5 M KHCO3
From Table 3 it can be concluded that the electro-deposited Sn cat-
alysts were of great potential towards CO2 electrochemical reduc-
tion for both facile preparation and high catalytic activity.
5. Conclusions
To summarize, Sn electrode prepared by electro-deposition
method in this work exhibited high catalytic activity and selectiv-
ity towards CO2 electrochemical reduction. Tuning deposit current
density had a direct impact on both morphology and performance
of the electrodes. In KHCO3 aqueous solutions saturated with CO2,
the maximum Faradaic efficiency for HCOOH production was over
91% at 1.4 V vs. SCE.
Acknowledgements
The research was supported by the Program for Changjiang
Scholars and Innovative Research Team in University (IRT-
13026). The authors would also like to thank the financial support
provided by the Open Research Fund Program of Key Laboratory of
Advanced Reactor Engineering and Safety, Ministry of Education of
China.
References
[1] T.R. Karl, K.E. Trenberth, Modern global climate change, Science 302 (2003)
1719–1723.
[2] J. Qiao, Y. Liu, F. Hong, J. Zhang, A review of catalysts for the electroreduction of
carbon dioxide to produce low-carbon fuels, Chem. Soc. Rev. 43 (2013) 631–
675.
[3] S. Kaneco, Y. Ueno, H. Katsumata, T. Suzuki, K. Ohta, Electrochemical reduction
of CO2 in copper particle-suspended methanol, Chem. Eng. J. 119 (2006) 107–
112.
[4] L.Q. Ye, X.L. Jin, X.X. Ji, C. Liu, Y.R. Su, H.Q. Xie, C. Liu, Facet-dependent
photocatalytic reduction of CO2 on BiOI nanosheets, Chem. Eng. J. 291 (2016)
39–46.
[5] S. Kaneco, K. Liba, H. Katsumata, T. Suzuki, K. Ohta, Electrochemical reduction
of high pressure carbon dioxide at a Cu electrode in cold methanol with CsOH
supporting salt, Chem. Eng. J. 128 (2007) 47–50.
[6] M. Alvarez-Guerra, S. Quintanilla, A. Irabien, Conversion of carbon dioxide into
formate using a continuous electrochemical reduction process in a lead
cathode, Chem. Eng. J. 207–208 (2012) 278–284.
[7] P.Q. Li, X.N. Sui, J.F. Xu, H. Jing, C.X. Wu, H. Peng, J. Lu, H.Z. Yin, Worm-like InP/
TiO2 NTs heterojunction with unmatched energy band photo-enhanced
electrocatalytic reduction of CO2 to methanol, Chem. Eng. J. 247 (2014) 25–32.
[8] C.C. Zhao, J.L. Wang, J.B. Goodenough, Comparison of electrocatalytic reduction
of CO2 to HCOOH with different tin oxides on carbon nanotubes, Electrochem.
Commun. doi:http://dx.doi.org/10.1016/j.elecom.2016.01.019.
[9] C.C. Zhao, Z.S. Yin, J.L. Wang, Efficient electrochemical conversion of CO2 to
HCOOH using Pd-polyaniline/CNT nanohybrids prepared in situ,
Chemelectrochem 2 (12) (2015) 1974–1982.
169
Maximum faradaic efficiency Refs.
>80%, 0.6 V vs. RHE [36]
>91%, 1.8 V vs. Ag/AgCl [22]
>93%, 1.8 V vs. SCE [21]
60%, 1.8 V vs. SCE [43]
72%, 1.6 V vs. SCE [19]
70%, 1.6 V vs. NHE [15]
64%, 1.2 V vs. Ag/AgCl [14]
58%, 0.7 V vs. RHE [12]
18%, 1.6 V vs. Ag/AgCl [18]
80%, 1.9 V vs. SCE [11]
86% at 1.3 kA m2 [25]
83.4%, 1.36 V vs. RHE [38]
92.6%, 2 V [44]
86.75 ± 2.89%, 1.8 V vs. Ag/AgCl [45]
[10] B. Innocent, D. Pasquier, F. Ropital, F. Hahn, J.M. Léger, K.B. Kokoh, FTIR
spectroscopy study of the reduction of carbon dioxide on lead electrode in
aqueous medium, Appl. Catal. B 94 (2010) 219–224.
[11] A.S. Agarwal, Y. Zhai, D. Hill, N. Sridhar, The electrochemical reduction of
Carbon Dioxide to formate/formic acid: engineering and economic feasibility,
ChemSusChem 4 (2011) 1301–1310.
[12] Y. Chen, M.W. Kanan, Tin oxide dependence of the CO2 Reduction efficiency on
tin electrodes and enhanced activity for tin/tin Oxide thin-film catalysts, J. Am.
Chem. Soc. 134 (2012) 1986–1989.
[13] Q. Wang, H. Dong, H. Yu, Fabrication of a novel tin gas diffusion electrode for
electrochemical reduction of carbon dioxide to formic acid, RSC Adv. 4 (2014)
59970–59976.
[14] J. Wu, F.G. Risalvato, S. Ma, X. Zhou, Electrochemical reduction of carbon
dioxide III. The role of oxide layer thickness on the performance of Sn electrode
in a full electrochemical cell, J. Mater. Chem. A 2 (2014) 1647.
[15] G.K.S. Prakash, F.A. Viva, G.A. Olah, Electrochemical reduction of CO2 over Sn-
NafionÒ coated electrode for a fuel-cell-like device, J. Power Sources 223
(2013) 68–73.
[16] F.K. Leli, T. Atilan, N. Palamut, A.M. Gizir, R. Aydin, C.H. Hamann,
Electrochemical reduction of CO2 at Pb- and Sn-electrodes in a fixed-bed
reactor in aqueous K2CO3 and KHCO3 media, J. Appl. Electrochem. 33 (2003)
447–450.
[17] P. Bumroongsakulsawat, G.H. Kelsall, Effect of solution pH on CO: formate
formation rates during electrochemical reduction of aqueous CO2 at Sn
cathodes, Electrochim. Acta 141 (2014) 216–225.
[18] R.L. Machunda, H. Ju, J. Lee, Electrocatalytic reduction of CO2 gas at Sn based
gas diffusion electrode, Curr. Appl. Phys. 11 (2011) 986–988.
[19] J. Wu, P.P. Sharma, B.H. Harris, X. Zhou, Electrochemical reduction of carbon
dioxide: IV dependence of the Faradaic efficiency and current density on the
microstructure and thickness of tin electrode, J. Power Sources 258 (2014)
189–194.
[20] J. Wu, F. Risalvato, X. Zhou, Electrochemical reduction of Carbon Dioxide I.
effects of the electrolyte on the selectivity and activity with Sn electrode, ECS
Trans. 41 (2012) 49–60.
[21] S. Zhang, P. Kang, T.J. Meyer, Nanostructured tin catalysts for selective
electrochemical reduction of carbon dioxide to formate, J. Am. Chem. Soc. 136
(2014) 1734–1737.
[22] W. Lv, R. Zhang, P. Gao, L. Lei, Studies on the faradaic efficiency for
electrochemical reduction of carbon dioxide to formate on tin electrode, J.
Power Sources 253 (2014) 276–281.
[23] A. Katoh, H. Uchida, M. Shibata, M. Watanabe, Design of electrocatalyst for CO2
reduction v effect of the microcrystalline structures of Cu-Sn and Cu-Zn alloys
on the electrocatalysis of CO2 reduction, J. Electrochem. Soc. 141 (1994) 2054–
2058.
[24] A. Schizodimou, G. Kyriacou, Acceleration of the reduction of carbon dioxide in
the presence of multivalent cations, Electrochim. Acta 78 (2012) 171–176.
[25] H. Li, C. Oloman, Development of a continuous reactor for the electro-
reduction of carbon dioxide to formate – Part 1: Process variables, J. Appl.
Electrochem. 36 (2006) 1105–1115.
[26] M. Gao, X. Chen, H. Pan, L. Xiang, F. Wu, Y. Liu, Ultrafine SnO2 dispersed carbon
matrix composites derived by a sol–gel method as anode materials for lithium
ion batteries, Electrochim. Acta 55 (2010) 9067–9074.
[27] W. Pu, X. He, J. Ren, C. Wan, C. Jiang, Electro-deposition of Sn–Cu alloy anodes
for lithium batteries, Electrochim. Acta 50 (2005) 4140–4145.
[28] A.S. Varela, C. Schlaup, Z.P. Jovanov, P. Malacrida, S. Horch, I.E.L. Stephens, I.
Chorkendorff, CO2 electroreduction on well-defined bimetallic surfaces: Cu
overlayers on Pt(111) and Pt(211), J. Phys. Chem. C 117 (2013)
20500–20508.
[29] M.R. Buchner, F. Kraus, H. Schmidbaur, Pyrophosphate complexation of tin(II)
in aqueous solutions as applied in electrolytes for the deposition of tin and tin
alloys such as white bronze, Inorg. Chem. 51 (2012) 8860–8867.
170 C. Zhao, J. Wang / Chemical Engineering Journal 293 (2016) 161–170
[30] A.N. Correia, M.X. Facanha, P. Lima-Neto, Cu-Sn coatings obtained from
pyrophosphate-based electrolytes, Surf. Coat. Technol. 201 (2007) 7216–7221.
[31] Q.N. Wang, H. Dong, H.B. Yu, Development of rolling tin gas diffusion
electrolyte, J. Power Sources 227 (2014) 278–284.
[32] S.M. Zhou, Electro-Deposition of Metals, Shanghai Scientific & Technical
Publishers (1987) (in Chinese).
[33] M. Avrami, Kinetics of phase change III Granulation, phase change, and
microstructure, J. Chem. Phys. 9 (1941) 177.
[34] R.L. Machunda, J. Lee, J. Lee, Microstructural surface changes of
electrodeposited Pb on gas diffusion electrode during electroreduction of
gas-phase CO2, Surf. Interface Anal. 42 (2010) 564–567.
[35] Y. Hori, S. Suzuki, Electrolytic reduction of bicarbonate ion at a mercury
electrode, J. Electrochem. Soc. 130 (1983) 2387–2390.
[36] S. Lee, J.D. Ocon, Y. Son, J. Lee, Alkaline CO2 electrolysis toward selective and
continuous HCOO production over SnO2 nanocatalysts, J. Phys. Chem. C 119
(2015) 4884–4890.
[37] C. Nayral, E. Viala, P. Fau, F. Senocq, J. Jumas, A. Maisonnat, Synthesis of tin and
tin oxide nanoparticles of low size dispersity for applicaion in gas sensing,
Chem-Eur. J. 6 (2000) 4082–4090.
[38] D.H. Won, C.H. Choi, J.H. Chung, M.W. Chung, E.H. Kim, S.I. Woo, Rational
design of a hierarchical tin dendrite electrode for efficient electrochemical
reduction of CO2, Chemsuschem 8 (2015) 3092–3098.
[39] M. Pourbaix, Atlas of Electrochemical Equilibria in Aquaeous Solutions,
National Association of Corrosion Engineers, Houston, USA, 1974.
[40] K. Ohta, A. Hasimoto, T. Mizuno, Electrochemical reduction of carbon dioxide
by the use of copper tube electrode, Energy Convers. Manage. 36 (1995) 625–
628.
[41] C.W. Li, M.W. Kanan, CO2 reduction at low overpotential on Cu electrodes
resulting from the reduction of thick Cu2O films, J. Am. Chem. Soc. 134 (2012)
7231–7234.
[42] S. Kapusta, N. Hackerman, The reduction of carbon dioxide and formic acid on
tin and indium elecrodes, J. Electrochem. Soc. 130 (1983) 608–613.
[43] Anawati, G.S. Frankel, A. Agarwal, N. Sridhar, Degradation and deactivation of
Sn catalyst used for CO2 reduction as function of overpotential, Electrochim.
Acta 133 (2014) 188–196.
[44] V.S.K. Yadav, M.K. Purkait, Electrochemical reduction of CO2 to HCOOH on a
synthesized Sn electrocatalyst using a Co3O4 anode, RSC Adv. 5 (2015) 68551–
68557.
[45] Q.N. Wang, H. Dong, H. Yu, H.B. Yu, Enhanced performance of gas diffusion
electrode for electrochemical reduction of carbon dioxide to formate by adding
polytetrafluoroethylene into catalyst layer, J. Power Sources 279 (2015) 1–5.