SCIENCE CHINA

Chemistry
•  ARTICLES  • February 2018   Vol.61   No.2: 228–235
https://doi.org/10.1007/s11426-017-9118-6

Selective electroreduction of carbon dioxide to formic acid on

electrodeposited SnO2@N-doped porous carbon catalysts
Lu Lu1,2, Xiaofu Sun1,2*, Jun Ma1, Qinggong Zhu1, Congyi Wu1, Dexin Yang1,2 & Buxing Han1,2*
1
Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Colloid and Interface and Thermodynamics, CAS
Research/Education Center for Excellence in Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China
2
School of Chemistry and Chemical Engineering, University of Chinese Academy of Sciences, Beijing 100049, China

Received July 3, 2017; accepted August 2, 2017; published online November 20, 2017

Electrocatalytic reduction of CO2 is a promising route for energy storage and utilization. Herein we synthesized SnO2 nanosheets
and supported them on N-doped porous carbon (N-PC) by electrodeposition for the first time. The SnO2 and N-PC in the
SnO2@N-PC composites had exellent synergistic effect for electrocatalytic reduction of CO2 to HCOOH. The Faradaic efficiency
of HCOOH could be as high as 94.1% with a current density of 28.4 mA cm−2 in ionic liquid-MeCN system. The reaction
mechanism was proposed on the basis of some control experiments. This work opens a new way to prepare composite electrode
for electrochemical reduction of CO2.

CO2 reduction, electrocatalyst, ionic liquid, porous carbon, green chemistry

Citation: Lu L, Sun X, Ma J, Zhu Q, Wu C, Yang D, Han B. Selective electroreduction of carbon dioxide to formic acid on electrodeposited SnO2@N-doped
porous carbon catalysts. Sci China Chem, 2018, 61: 228–235, https://doi.org/10.1007/s11426-017-9118-6

1   Introduction
Carbon dioxide (CO2) is the main greenhouse gas released by
the excessive burning of fossil fuels, but it is also a cheap,
non-toxic, and abundant C1 feed stock [1–10]. To date, be-
sides CO2 sequestration and storage, some approaches have
been achieved for CO2 conversion, including electrochemi-
cal, photocatalytic and direct catalytic conversions. Among
these ongoing attempts, electrochemical reduction of CO2 is
a promising process to produce a series of valuable chem-
icals under mild conditions, of which the efficiency can be
easily controlled by different parameters, such as electrode
materials, electrolytes, and applied potentials [11–14]. Many
electrocatalysts, including metals, metal oxides and carbon-
based materials have been investigated for CO2 reduction to
*Corresponding authors (email: sunxiaofu@iccas.ac.cn; hanbx@iccas.ac.cn)
© Science China Press and Springer-Verlag GmbH Germany 2017
value-added chemicals and carbon-based fuels in the past few
decades.
In particular, the selective conversion of CO2 into formic
acid (HCOOH) has received much attention, which is a two-
electron reaction process and simple CO2 reduction pathway.
HCOOH is widely used in leather and tanning industry, an-
imal feed additives, as well as the precursor for producing
other valuable chemicals [15,16]. Some composite materials
such as noble metal nanoparticles, transition metal oxides and
metal complexes have been applied as electrodes [17–24].
However, it is still highly desirable to achieve high selectiv-
ity, satisfactory CO2 conversion rate and low overpotential for
HCOOH production on cheap electrodes.
Recently, noble-metal-free electrocatalysts have received
much interest because of their low cost, environmentally be-
nign, and outstanding thermal stability [25–27]. Zeolitic im-
idazolate frameworks (ZIFs) are a new class of porous crys-
tals with extended three-dimensional structures constructed
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Lu et al.   Sci China Chem   February (2018)  Vol.61  No.2
from tetrahedral metal ions (e.g., Zn, Co) bridged by imida-
zolate [28,29]. The chemical and thermal stability of ZIFs
permit many applications, such as selective separation from
industrial gas mixtures and the capture of CO2. Due to their
highly microporous structure and regular morphology, ZIFs
have been demonstrated to be one of the attractive carbon pre-
cursors to prepare N-doped porous carbon (N-PC) materials
[30–33]. N-PC leads to the formation of a nanoporous carbon
structure with high specific surface area and good electrical
conductivity.
As an inexpensive and earth-abundant metal, Sn can be
used for selective CO2 electroreduction to HCOOH [34].
However, the activity of Sn is low for practical application
due to the low current density and high over potential. To
improve the catalytic activity of Sn, herein we propose a
novel approach to electrodeposit ultrathin SnO2 nanosheets
on N-PC. The loadings of SnO2 could be controlled by
the electrophoretic deposition (EPD) time. For clarity,
(SnO2)x@N-PC/carbon paper (CP) was used to represent
the as-prepared working electrodes, where x is used to
represent the EPD time (min). It was discovered that
(SnO2)90@N-PC/CP electrode was the most efficient for
selective electroreduction of CO2 to HCOOH when MeCN
containing 0.5 M ionic liquid (IL), 1-butyl-3-methylimida-
zolium hexafluorophosphate ([Bmim]PF6) was used as the
electrolyte. The Faradaic efficiency of HCOOH production
could reach 94.1% with a current density of 28.4 mA cm−2 at
a moderate over potential of 0.31 V, demonstrating very high
catalytic activity among the literature reported up to date
(Table S1, Supporting Information online).
2   Experimental
2.1   Materials
SnCl2·2H2O (purity>99%) and Zn(NO3)2·6H2O (pu-
rity>99%) were provided by Sinopharm Chem. Reagent
Co. Ltd. (China). Ethylenediamine (purity>99%)
and N,N-dimethylformamide (DMF, purity>99%) were
purchased from Beijing Chemical Company (China).
2-Methylimidazole (purity>99%) were obtained from TCI
(Japan). Graphene oxide (GO) was obtained from Institute
of Coal Chemistry, Chinese Academy of Sciences. Ionic
liquids: 1-butyl-3-methylimidazolium tetrafluoroborate
([Bmim]BF4, purity>99%), 1-butyl-3-methylimidazolium
hexafluorophosphate ([Bmim]PF6, purity>99%), 1-butyl-3-
methylimidazolium perchlorate ([Bmim]CIO4, purity>99%),
1-butyl-3-methylimidazolium nitrate ([Bmim]NO3, pu-
rity>99%), 1-butyl3-methylimidazolium bis(trifluo-
romethylsulfonyl)imide ([Bmim]Tf2N, purity>99%) and
1-butyl-3-methylimidazolium trifluoromethanesulfonate
([Bmim]CF3SO3, purity>99%) were purchased from the
229
Centre of Green Chemistry and Catalysis, Lanzhou Insti-
tute of Chemical Physics, Chinese Academy of Sciences.
Toray carbon paper (CP, TGP-H-60, 19 cm×19 cm), Nafion
D-521 dispersion (5% w/w in water and 1-propanol, ≥0.92
meg g–1 exchange capacity) and Nafion N-117 membrane
(0.180 mm thick, ≥0.90 meg g−1 exchange capacity) were
purchased from Alfa Aesar China Co., Ltd. (USA).
2.2   Synthesis of thin SnO2 sheets
The procedures were similar to that reported by other au-
thors [35]. In a typical experiment, 0.5 mmol SnCl2·2H2O
was added into 40 mL ethylenediamine initially. After inten-
sively stirring for 30 min, the mixture was transferred into a
50 mL Teflon-lined autoclave, sealed and heated at 180 °C for
48 h. The system was then allowed to cool down to room
temperature. The final product was collected by centrifuging
the mixture and washed with distilled water (3´30 mL) and
ethanol (3´30 mL), and then dried overnight under vacuum
for further use.
2.3   Synthesis of nitrogen-doped porous carbon (N-PC)
The procedures were similar to that reported by other authors
[36]. 0.366 g of Zn(NO3)2·6H2O and 0.811 g of 2-methylim-
idazole were dissolved in 12 and 20 mL of methanol,
respectively. Next, Zn(NO3)2 solution (12 mL) was added
into the 2-methylimidazole solution to obtain a clear solution.
8 mL of GO solution (1 mg mL−1 in water/methanol, 1:4, v/v)
was added to the above mixed solution immediately. After
stirring for 3 h, the precipitation was collected by centrifu-
gation (10000 r min−1 for 5 min) and washed with methanol
(3´30 mL). After drying at 50 °C for 12 h, ZIF/GO compos-
ite was obtained. The composite was calcined at 800 °C for
3 h in Ar atmosphere. Then the obtained material was dis-
persed in 2 M HCl aqueous solution for 12 h and collected
by centrifugation and washed with water (3´30 mL). After
drying at 80 °C for 24 h, N-PC was obtained.
2.4   Electrophoretic deposition of N-PC/CP with thin
SnO2 sheets
The N-PC was suspended in ethanol with Nafion D-521
dispersion (5 wt%) to form a homogeneous ink, which was
spreaded onto one side of the CP to obtain N-PC/CP elec-
trode. Then, the commonly used electrophoretic deposition
method [37] was applied to fabricate (SnO2)x@N-PC/CP
electrodes. 40 mg of SnO2 powder were suspended in
20 g binary mixtures (water/DMF, 1:4, m/m) and sonicated
for 30 s. Two N-PC/CP electrodes were dipped in the de-
position solution (1 cm separation distance). A constant
DC voltage of 30 V was applied. (SnO2)x@N-PC/CP was
obtained after suitable time (x denotes the deposition time
(min)).
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Lu et al.   Sci China Chem   February (2018)  Vol.61  No.2
2.5   Materials characterization
X-ray photoelectron spectroscopy (XPS) analysis was
performed on the Thermo Scientific ESCA Lab 250Xi
(USA) using 200 W monochromatic Al Kα radiation. The
500 μm X-ray spot was used for XPS analysis. The base pres-
sure in the analysis chamber was about 3×10−10 mbar. Typi-
cally, the hydrocarbon C1s line at 284.8 eV from adventitious
carbon was used for energy referencing. Powder X-ray
diffraction (PXRD) patterns were collected on the X-ray
diffractometer (Model D/MAX2500, Rigaka, Japan) with
Cu Kα radiation. The morphologies of (SnO2)x@N-PC/CP
electrodes were characterized by a HITACHI S4800 (Japan)
scanning electron microscope (SEM) and JEOL-2100F
(Japan) transmission electronmicroscopy (TEM) operated at
200 kV. The thin SnO2 sheets were characterized by infrared
spectra (IR) spectroscopy with a Bruker Tensor 27 spec-
trometer (Germany). Acquisition was accomplished using
an accumulation rate of 32 scans at 25 °C in the spectral
range of 400 to 4600 cm−1. The nitrogen adsorption/des-
orption isotherms of porous carbon were determined using
a Quadrasorb SI-MP system (Quantachrome Instrument,
USA). Surface areas were calculated from the adsorption
data using Brunauer-Emmett-Teller (BET) methods.
2.6   Linear sweep voltammetry (LSV) study and electrol-
ysis experiments
The electrochemical workstation (CHI 6081E, Shanghai CH
Instruments Co., China) was used in the experiments of CO2
reduction. LSV measurements were carried out in a single
compartment cell with three-electrode configuration, which
contained (SnO2)x@N-PC/CP working electrode, an Ag/Ag+
(0.01 M AgNO3 in 0.1 M TBAP-MeCN) reference electrode
and a platinum gauze auxiliary electrode. CO2 or N2 satu-
rated solution were obtained by bubbling with CO2 or N2 for
30 min.
The LSV measurement in gas-saturated electrolyte was
conducted in the potential range between −1.0 and −2.5 V
(vs. Ag/Ag+) at a sweep rate of 20 mV s−1. Slight magnetic
stirring was applied in the process. The electrolysis experi-
ments were conducted at 25 °C in a typical H-type cell that
was similar to that used in our previous works [38,39]. In the
experiments, the cathode and anode compartments were sep-
arated by a Nafion 117 proton exchange membrane. H2SO4
aqueous solution (0.5 M) was used as anodic electrolyte.
The proton source was from the electrolysis of water and
H+ could be transferred from anode compartment to cathode
compartment through Nafion 117 proton exchange mem-
brane. In a typical experiment, CO2 was bubbled through the
catholyte (2 mL min−1) for 30 min before electrolysis. Then,
potentiostatic electrochemical reduction of CO2 was carried
out with CO2 bubbling (2 mL min−1).
3   Results and discussion
The SnO2 sheets were prepared by the chemical reaction of
SnCl2·2H2O and ethylenediamine via one-pot solvothermal
reaction, according to the previous work [38]. TEM image in
Figure 1(A) shows a 2D graphene-like morphology of SnO2
nanosheet. The insert PXRD pattern shows that the as-pre-
pared SnO2 had a tetragonal structure, and the purity was fur-
ther verified by IR and XPS in Figure S1 and Figure S2 (Sup-
porting Information online), respectively. The correspond-
ing high-resolution TEM (HR-TEM) in Figure 1(B) exhibits
0.277 and 0.299 nm belong to the (101) plane and (200) plane
of SnO2, respectively.
The procedures to prepare the (SnO2)x@N-PC electrodes
are illustrated in Figure 2. Firstly, Zn salts in methanol were
added to the solution of imidazole. Zn2+ can coordinate with
imidazole to form metal/imidazole ZIF clusters, followed by
the addition of graphene oxide (GO). The ZIF clusters were
readily attached to the GO layer due to a strong interaction
between metal ions from ZIF and the oxygen groups on GO.
The composites of ZIF nanoparticles on GO was formed. The
N-PC was obtained after carbonization at 800 °C in the arat-
mosphere. Then, N-PC was suspended in ethanol with Nafion
D-521 dispersion (5 wt%) to form a homogeneous ink, which
was spread onto one side of the CP to obtain N-PC/CP elec-
trode. Next, EPD method was used to prepare (SnO2)x@N-
PC/CP electrode by dipping two electrodes in 20 g mixture
solution of H2O/DMF (m/m=1:4) with 40 mg SnO2 power.
SnO2 nanosheets can be easily deposited on N-PC/CP cath-
ode with lower voltage in a short time, and the main reason is
that SnO2 nanosheets have partial charge on the surface due to
the synthetic media [40]. By changing the time of deposition,
the loading of SnO2 could also be controlled (Figure S3).
During the carbonization process, N-PC remained the
nanosheet morphology (Figure 1(C)). The Brunauer-Em-
mett-Teller (BET) surface area of the N-PC was as high as
717.3 m2 g−1. XPS spectra (Figure 1(D) and Figure S4) show
the chemical state of N-PC surface. The high resolution N1s
spectra for N-PC were fitted with three peaks at about 400.6,
399.0 and 397.9 eV, corresponding to graphitic N, pyrrolic
N and pyridinic N, respectively. Their relative contents were
48.2%, 13.4% and 38.4%, respectively. It indicated that
pyrrolic N and pyridinic N species are dominant, which have
previously been shown to act as electrochemically active
species in the reduction of CO2 [39,41].
The morphologies of N-PC/CP and (SnO2)90@N-PC/CP
electrodes were also examined by SEM. As shown in
Figure 1(E), the electrodes are coated by an array of striated
sheets, which have smooth and nubby surfaces. However,
densely packed SnO2 was formed after a 90 min deposition.
The surface became highly textured with an obvious layer of
SnO2 (Figure 1(F)).
The CO2 reduction activities of  different  (SnO2)x@N-PC/
  
Lu et al.   Sci China Chem   February (2018)  Vol.61  No.2 231

   (A)
   
Figure 1    TEM image of SnO2 nanosheets. The inset shows powder XRD pattern of the SnO2 nanosheets. (B) HR-TEM image of SnO2 nanosheets. (C)
TEM image of N-PC. (D) XPS spectra of N 1s orbits of N-PC. Peaks a, b and c stand for graphitic N, pyrrolic N, and pyridinic N, respectively. (E) SEM image
of N-PC/CP electrode. (F) SEM image of (SnO2)90@N-PC/CP electrode. The insets in (E) and (F) show the thickness of electrodes (scale bar, 100 μm) (color
online).

   Schematic
   
Figure 2    illustration of the procedures to prepare the N-PC/CP and (SnO2)x@N-PC/CP electrodes (color online).
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Lu et al.   Sci China Chem   February (2018)  Vol.61  No.2

CP electrodes were investigated in MeCN containing 0.5 M
[Bmim]PF6, which is a widely used electrolyte [42]. The
experiments were conducted in a typical three-electrode
electrochemical H-cell [43,44]. The applied potential was
swept between −1.0 and −2.5 V (vs. Ag/Ag+) at a sweep
rate of 20 mV s−1 and the linear sweep voltammetry (LSV)
curves for (SnO2)90@N-PC/CP are shown in Figure 3(A). A
reduction peak at about −2.2 V vs. Ag/Ag+ can be observed
for the CO2-saturated system, while the current density at
−2.2 V vs. Ag/Ag+ in the N2-saturated system was negligi-
ble, indicating electrochemical reduction of CO2 occurred
over the (SnO2)90@N-PC/CP electrode. The LSV curves for
(SnO2)x@N-PC electrodes with different EPD times were
shown in Figure 3(B). The EPD time affected the current
density significantly. Different EPD times resulted in differ-
ent loadings of SnO2 on the N-PC support.
Among them, (SnO2)90@N-PC/CP showed highest cur-
rent density. Controlled potential electrolysis of CO2 was
then performed at −2.2V vs. Ag/Ag+ in the H-cell using
CO2-saturated MeCN containing 0.5 M [Bmim]PF6 as the
electrolyte. Under the reported reaction conditions, HCOOH
was the only liquid product as detected by NMR spec-
troscopy and H2 was gaseous product as determined by gas
chromatography (GC). 1H NMR spectra (Figure S5) showed
that there was no HCOOH signal when using N2-saturated
electrolyte, indicating that CO2 was the carbon source for
the product. Time curves of the electrolysis processes for
(SnO2)x@N-PC electrodes with different EPD times are
given in Figure 3(C), which shows that the current densities
did not decrease with time in the electrolysis, suggesting that
both the (SnO2)x@N-PC/CP electrode and the electrolyte
were stable. Moreover, the current density and Faradaic
efficiency of HCOOH on (SnO2)x@N-PC electrodes with
EPD times at −2.2V vs. Ag/Ag+ are shown in Figure 3(D).
The current density and Faradaic efficiency of HCOOH
increased with the EPD time in the range of 0–90 min. But
it was nearly independent of EPD after 90 min. Therefore,
CO2 reduction using (SnO2)90@N-PC/CP was further studied
and the results are discussed in the following.
Figure 4(a) shows the current density and Faradaic effi-
ciency for HCOOH on (SnO2)90@N-PC electrode in MeCN
containing 0.5 M [Bmim]PF6 with a 5 h electrolysis at
different applied potentials. The current density increased
continuously with the applied potential. However, the max-
imum HCOOH selectivity occurred at −2.2 V vs. Ag/Ag+,
due to that the competitive hydrogen-evolution reaction
(HER) become dominant at high potentials gradually.
The effect of [Bmim]PF6 content was investigated using
(SnO2)90@N-PC/CP electrode at −2.2 V vs. Ag/Ag+ in
Figure 4(b). It demonstrates that the current density increased
up to [Bmim]PF6 content of 0.5 M, and then decreased. A
probable reason was that the number of ionic species in
the electrolyte increases with increasing IL concentration.
Above 0.5 M of [Bmim]PF6  content,  the  enhanced  electro-

   (A)
   
Figure 3    LSV curves for (SnO2)90@N-PC/CP electrode in (a) N2-saturated and (b) CO2-saturated MeCN containing 0.5 M [Bmim]PF6. (B) LSV curves for
(SnO2)x@N-PC/CP electrodes with different EPD times in CO2-saturated MeCN containing 0.5 M [Bmim]PF6: (a) 0 min; (b) 30 min; (c) 60 min; (d) 90 min. (C)
Time curves of the electrolysis processes for (SnO2)x@N-PC/CP electrodes with different EPD times at −2.2 V vs. Ag/Ag+ in CO2-saturated MeCN containing
0.5 M [Bmim]PF6: (a) 0 min; (b) 30 min; (c) 60 min; (d) 90 min. (D) Current density and Faradaic efficiency of HCOOH on (SnO2)x@N-PC electrodes with
EPD times at −2.2 V vs. Ag/Ag+ in CO2-saturated MeCN containing 0.5 M [Bmim]PF6 with a 5 h electrolysis (color online).
  
Lu et al.   Sci China Chem   February (2018)  Vol.61  No.2 233

   (a)
    Current density and Faradaic efficiency of HCOOH at different applied potentials on (SnO2)90@N-PC/CP electrode in MeCN containing 0.5 M
Figure 4   
[Bmim]PF6 with a 5 h electrolysis. (b) Current density and Faradaic efficiency of HCOOH on (SnO2)90@N-PC/CP electrode at −2.2 V vs. Ag/Ag+ in MeCN
with different [Bmim]PF6 concentrations with a 5 h electrolysis. (c) Current density and Faradaic efficiency of HCOOH on (SnO2)90@N-PC/CP electrode at
−2.2 V vs. Ag/Ag+ in MeCN containing 0.5 M different ILs with a 5 h electrolysis. (d) Tafel plot for HCOOH production over (SnO2)90@N-PC/CP in MeCN
containing 0.5 M [Bmim]PF6 (color online).

static attraction between the anions and cations reduces the
charge transfer rate. [Bmim]PF6 play a catalytic role on the
CO2 reduction via the stabilization of reaction intermediate,
so IL can be also recognized as a homogeneous electrocata-
lyst [45]. The competition of these factors results in the max-
imum current density at 0.5 M.
We also performed the electrochemical reduction in
CO2-saturated MeCN containing 0.5 M various ILs in
Figure 4(c). The two commonly used ILs [Bmim]PF6
and 1-butyl-3-methylimidazolium tetrafluoroborate
([Bmim]BF4) exhibited much higher current densities and
Faradaic efficiencies, which results partially from the strong
interaction between CO2 and fluorine containing ILs [46].
These control experiments demonstrated that the conversion
rate of CO2 was the highest in [Bmim]PF6. In contrast, the
ILs without fluorine, such as 1-butyl-3-methylimidazolium
nitrate ([Bmim]NO3), yielded lower current densities and
lower Faradaic efficiency of HCOOH. This observation
indicates that anions played an important role in the electro-
chemical reduction of CO2. We also compared the catalytic
performance of (SnO2)90@N-PC/CP electrode in 0.5 M
KHCO3 aqueous electrolyte. The highest Faradaic efficiency
of HCOOH production in 0.5 M KHCO3 aqueous solution
could only reach 15.2% and the main product was H2. Be-
sides, Figure 4(d) shows the variation of overpotential with
partial current density. The plot is linear in the overpotential
range of 0.06–0.11 V with a slope of 104.4 mV dec−1. This
slope is consistent with a rate-determining initial electron
transfer to CO2 to form a surface adsorbed CO2• − intermedi-
ate, which is a commonly accepted mechanism over metal
electrodes [47].
To obtain further mechanistic insight, we investigated the
roles of SnO2 and N-PC in the electrochemical reduction of
CO2 to HCOOH, respectively. It was found that very small
amount of HCOOH was formed over N-PC electrode at
−2.2 V vs. Ag/Ag+ in CO2-saturated MeCN containing 0.5 M
[Bmim]PF6 with a 5 h electrolysis. By replacing the support
with carbon black (C), we also prepared (SnO2)90@C/CP
electrode using EPD method. Under the same conditions,
when (SnO2)90@C/CP was used as the working electrode
for CO2 reduction, the Faradaic efficiency of HCOOH was
only about 24%. H2 becomes the main product, which may
be that the rate of mass transport of H+ is faster than CO2
when carbon black was used as support. Obviously, the high
performance of (SnO2)90@N-PC/CP electrode is attributed to
the synergistic effect between SnO2 and N-PC support in the
IL-based electrolyte. N-PC has been reported as an effective
CO2 adsorbing material due to some defect sites and the
polarized C atoms induced by adjacent N atoms [48].
The resulting positively charged C atoms can also facilitate
the formation of CO2• − intermediate [49]. In this process,
the presence of [Bmim]+ and CO2 can form a complex
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Lu et al.   Sci China Chem   February (2018)  Vol.61  No.2

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