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Surface structure-dependent electrocatalytic

reduction of CO2 to C1 products on SnO2 catalysts†
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Cite this: DOI: 10.1039/c9se00678h

Minling Fang,a Zhiping Zheng,a Jiayu Chen,a Qian Chen,a Deyu Liu,c Binbin Xu,a
Jianyang Wu,a Qin Kuang *a and Zhaoxiong Xie *ab

Received 19th August 2019
Accepted 2nd December 2019
DOI: 10.1039/c9se00678h
rsc.li/sustainable-energy
An alternative way to mitigate the energy and environmental crisis is electrochemical CO2 reduction (ECR)
into high-value products using renewable energy. Recently, Sn-based catalysts have attracted attention
because of their high ECR selectivity to C1 products (HCOOH and CO). However, high overpotential, low
current density, and poor stability are some issues that need to be addressed for these Sn based ECR
catalysts. Resolving these problems largely depends on a comprehensive insight into the relationship
between the structure and the performance of the catalysts in the ECR. In this work, we specifically
compared the ECR activities and selectivities of three kinds of SnO2 nanocrystals (NCs) with different
dominantly exposed facets ({111}, {221} and {110}) in an effort to elucidate their surface structure–
performance relationship. We found that {111} faceted octahedral SnO2 NCs (i.e., Oct-{111} NPs) showed
not only high selectivity for C1 products (>90% FE) in a wide potential range of
0.7 V to
1.0 V but also
significant stability. The performance of Oct-{111} NPs was superior to that of the other two SnO2
morphologies, i.e. {221} faceted SnO2 octahedral NCs and {110}-dominantly faceted SnO2 rod-like NCs.
Detailed structure and composition analysis revealed that such different ECR performances of the three
SnO2 facets were mainly related to the formation of different catalytic layers on their surfaces. The
findings presented here will deepen our understanding of the surface-dependent performances of Sn-
based electrocatalysts in the ECR. This work provides a new strategy to construct high performance
electrocatalysts through rational regulation of the metal/oxide interface.

in enhancing catalyst activity, selectivity, and stability because

Introduction
With the rapid development of industry and society, global
warming caused by the vast amount of fossil energy consump-
tion and the consequent energy crisis are becoming increas-
ingly serious.1 Converting CO2 into useful chemicals and fuels
using renewable energy resources seems to be a promising
solution.2 Over the past few decades, a number of catalysts
including metals,3–5 transition-metal oxides,6–8 transition-metal
chalcogenides,9,10 etc. have been used for electrochemical CO2
reduction (ECR).11,12 To achieve high performances, various
construction strategies have been proposed. Among them,
surface engineering techniques (e.g., crystal surface effect4,13,14
and surface modication14–16) have proven to be highly effective
a
State Key Laboratory of Physical Chemistry of Solid Surfaces, Department of
Chemistry, College of Chemistry and Chemical Engineering, Xiamen University,
Xiamen 361005, P. R. China. E-mail: qkuang@xmu.edu.cn; zxxie@xmu.edu.cn; Fax:
+86-592-2183047
b
Pen-Tung Sah Institute of Micro-Nano Science and Technology, Xiamen University,
Xiamen 361005, China
c
Ningbo Institute of Materials Technology & Engineering, Chinese Academy of Sciences,
1219 Zhongguan West Road, Ningbo 315201, China
† Electronic supplementary information (ESI) available. See DOI:
10.1039/c9se00678h
of the high sensitivity of ECR to the surface structure. For
instance, Woo et al. found that the Zn (101) facet is favourable
for CO formation while the Zn (002) facet favours H2 evolution
during ECR.17 Similarly, Yin and co-workers proposed that the
selectivity toward CH4, C2H4, C2H6, and C3H8 was higher on Cu
(110) facets than on Cu (100) facets.18
Recently, low-cost and environmentally friendly Sn-based
catalysts have attracted attention due to their decent ECR
performance in obtaining HCOOH, which is usable as a fuel in
formic acid fuel cells.7,19,20 Various strategies to further enhance
the ECR performances of Sn-based catalysts, including grain
boundary engineering,21 size and morphology regulation,22,23
and so on, have been proposed. Notably, based on theoretical
calculations, and electro-kinetic and in situ Raman spectral
analyses, researchers have found that the presence of SnOx in
Sn-based electrocatalysts plays a critical role in ECR, activating
CO2 to CO$
2

2 and CO3 , which are important intermediates for

24–27
generating HCOO . In spite of this progress, systematic
studies are still urgently needed to reveal the surface structure–
performance relationships of Sn-based ECR catalysts. Espe-
cially, the inuence of exposed facets of catalysts on the
formation of the Sn/SnO2 catalytic layer in the ECR process
cannot be ignored.

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Herein, SnO2 catalysts with well-dened surface structures
were used to explore the internal relationship between their
surface structures and ECR performances. Three kinds of SnO2
nanocrystals (NCs) with different exposed crystal surfaces were
specically synthesized for this purpose. Then, the changes in
the ECR performances of SnO2 catalysts with different crystal
surfaces were investigated. Studies revealed that Sn nano-
particles were reduced in situ on the SnO2 NCs in the ECR
process and the status of the newly formed Sn/SnO2 interfaces
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was the key factor affecting the ECR performance of SnO2
catalysts. Among the three catalysts, the octahedral SnO2 NCs
(Oct-{111}) with exposed {111} facets can form more Sn/SnO2
catalytic interfaces in the ECR process, and thus show better
catalytic performance. Strikingly, it was observed that the
Faraday efficiency (FE) for C1 products (CO and HCOOH) sur-
passed 90% in a wide range of potentials from
0.7 V to
1.0 V
vs. the reversible hydrogen electrode (RHE).
Results and discussion
Three kinds of SnO2 NCs with exposed {111}, {221}, and {110}
facets, respectively (denoted as Oct-{111}, Oct-{221}, and Rod-
{110}) were synthesized based on previously reported
methods.28,29 Powder X-ray diffraction (XRD) analysis revealed
that all the SnO2 samples exhibited a pure rutile phase (JCPDS
no. 41-1445) without the presence of any impurities (Fig. 1a).
The morphology of these samples was studied by scanning
electron microscopy (SEM). Both Oct-{111} and Oct-{221} dis-
played an octahedral shape, and their particle sizes were mainly
distributed within 100–250 nm and 150–200 nm, respectively
(Fig. 1b and c). However, the tip angles of the Oct-{111} and Oct-
{221} SnO2 NCs were different, as they were actually enclosed by
different facets.19 The Rod-{110} NCs displayed a tetragonal rod-
like shape with two pyramidal tips, and the average ratio of
length to diameter was approximately 4 (Fig. 1d). According to
a previous study,28 the side surfaces of Rod-{110} NCs were
enclosed by stable {110} facets and the two pyramidal tips were
surrounded by {221} facets.
Surface scientists have demonstrated that the average
surface energy of rutile SnO2 is 2.280 J m
2 for {221}, 2.209 J m
2
for {111}, and 1.401 J m
2 for {110}.30 Fig. 1e–g show the sche-
matic models of atomic arrangement on rutile SnO2 (111), (221),
Fig. 1 (a) XRD patterns and (b–d) SEM images of Oct-{111}, Oct-{221},
and Rod-{110}; inset: schematic model of an ideal SnO2. (e–g) Sche-
matic models of atomic arrangement on the (111), (221), and (110)
surfaces, respectively.
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and (110) surfaces. Sn atoms in the bulk of rutile SnO2 are
sixfold-coordinated by O atoms, while Sn atoms at the surface
are usually coordinatively unsaturated. On the (111) and (221)
surfaces, Sn atoms are located at vefold coordinated sites
(blue) with one dangling bond and fourfold-coordinated sites
(purple) with two dangling bonds. As the most stable facets, the
rutile (110) surface contains rows of sixfold-coordinated Sn
atoms (grey) and vefold-coordinated Sn atoms (blue) with one
dangling bond perpendicular to the surface.30 It should be
pointed out that {221} high-index facets can be reconsidered as
a combination of (111) terraces and (110) steps. Clearly, the
difference in the surface structure would inuence the ECR
performances of the three morphologically distinct SnO2 NCs.
ECR tests were conducted in an H-type three-electrode
system (Fig. S1†). Carbon paper loaded with the three
prepared morphologically distinct SnO2 NCs (1 mg cm
2) acted
as a working electrode. Ag/AgCl and Pt (1  1 cm2) electrodes
were used as the reference electrode and counter electrode,
respectively. The ECR activities of the three morphologically
distinct SnO2 NCs were rst evaluated by linear scan voltam-
metry (LSV) in 0.5 M NaHCO3 aqueous solutions saturated with
N2 and CO2, respectively. As shown in Fig. 2a, all the SnO2
samples exhibited higher current intensities in the CO2 satu-
rated electrolyte than in the N2 saturated electrolyte, indicating
the catalytic activity of SnO2 NCs towards CO2 reduction. Note
that there was a cathodic peak in the potential range of 0 V to

0.4 V, which corresponds to the reduction of SnO2 (Fig. S2†).31
In the CO2-saturated electrolyte, the current densities of the
three samples at
1.0 V vs. RHE followed the order Rod-{110}
Fig. 2 (a) LSV curves of Oct-{111}, Oct-{221} and Rod-{110} catalysts in
N2- or CO2-saturated 0.5 M NaHCO3 aqueous solution at a scan rate
of 50 mV s
1. (b–d) Faradaic efficiencies of H2 (black), CO (red) and
HCOO
(blue) over the Oct-{111}, Oct-{221} and Rod-{110} catalysts at
various applied potentials, respectively. All the tests were conducted in
CO2-saturated 0.5 M NaHCO3 aqueous solution.
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(13 mA cm
2) > Oct-{111} (10.8 mA cm
2) > Oct-{221} (9.38 mA
cm
2). This result indicated that the ECR activities of the three
SnO2 samples were closely related to their exposed facets.
ECR tests were further conducted at selected potentials
between
0.6 and
1.0 V for 2 h in the CO2-saturated electro-
lyte, to determine the selectivity of the nal products. Both
gaseous and liquid products were analysed using gas chroma-
tography (GC) and 1H nuclear magnetic resonance (1H-NMR)
spectroscopy, respectively. The analysis results indicated that
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H2, CO, and formate were the major products. Fig. 2b–
d summarize the Faraday efficiency (FE) of the products
generated over the three SnO2 samples at the selected poten-
tials. Among these samples, the Oct-{111} showed the best
performance as the FE of C1 products (CO and HCOOH) was up
to 90% in the potential range of
0.7 V to
1.0 V. Over the Oct-
{111}, the hydrogen evolution reaction (HER) was remarkably
inhibited (the FE of H2 at the corresponding potentials was less
than 12%). Also, FEs of H2 and CO gradually decreased, while
that of the formate increased with an increase in reduction
potential. Thus it can be seen that the formation of formate was
more favorable over the Oct-{111} at relatively higher potentials.
Over the Oct-{221}, with an increase in applied potential, the FE
of H2 constantly decreased and the FEs of C1 products
remained between 60% and 70% at potentials from
0.7 V to

1.0 V. In contrast to the above results, the FE of H2 over the
Rod-{110} decreased initially and then started increasing with
an increase in the applied potential.
The chronoamperometric current curves of the three SnO2
samples at different potentials in CO2-saturated 0.5 M NaHCO3
aqueous solution were analysed to evaluate the stability of the
catalysts. As shown in Fig. 3a–c, the ECR current density for the
SnO2 catalysts had a strong positive correlation with the applied
potentials, consistent with the results of LSV. The current
density of all samples increased initially with reaction time
before attaining stability. It should be noted that the time for
Fig. 3 Chronoamperometric current (i–t) curves of (a) Oct-{111}, (b) Oct-{221} and (c) Rod-{110} at different potentials in CO2-saturated 0.5 M
NaHCO3 aqueous solution. Faradaic efficiency of H2 and CO for Oct-{111} at (d)
0.6, (e)
0.8, and (f)
1.0 V in CO2-saturated 0.5 M NaHCO3
aqueous solution.
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reaching a steady state was shorter when the applied voltage
was more negative. In particular, at the reduction potential of

1.0 V vs. RHE, the ECR activity of all three samples fell
dramatically with time aer the initial surge (2 h). Furthermore,
we tracked the FEs of the gas products at different times by GC
to explore the intrinsic reason behind this facet dependent ECR
activity. The FE of H2 drastically decreased in the rst 1 hour for
Oct-{111}, while the FE of CO increased and then reached
a plateau (Fig. 3d–f). In contrast to Oct-{111}, the FE of H2 over
the Oct-{221} and Rod-{110} at low potentials (
0.6 V vs. RHE)
increased as the reaction progressed (Fig. S3 and S4†). Similarly,
at other applied potentials (
0.8 and
1.0 V vs. RHE), the time-
dependent FE of gas products over the Oct-{221} and Rod-{110}
showed different trends from that over the Oct-{111}. The above
results indicated that the surface structure of the three
morphologically distinct SnO2 samples changed signicantly
during the ECR process.
The initial increase in currents might have been caused by
the partial reduction of the surface of SnO2 catalysts under
negative potentials. To conrm this the composition and
morphology of all three catalysts were further characterized
aer chronoamperometry tests. As analyzed above, some
diffraction peaks assigned to metallic Sn of a tetragonal phase
(JCPDS no. 65-2631) were detected in the XRD patterns of the
three catalysts used (Fig. S5†). Additionally, some particles of
the order of tens of nanometers were observed on the SnO2
catalyst surface in the SEM images (Fig. S6a and c†). Surpris-
ingly, the rod-like morphology of Rod-{110} NCs was almost
completely destroyed. In contrast, the Oct-{111} and Oct-{221}
samples retained their octahedral morphology. This result was
consistent with the more dramatic uctuations of the time-
dependent FE of the gas products in Rod-{110} as compared
to Oct-{111} and Oct-{221}. Thus, it can be deduced that the
structural stability of Rod-{110} NCs in ECR was far inferior to
that of Oct-{111} and Oct-{221}.
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High-angle annular dark eld-scanning transmission elec-

tron microscopy (HAADF-STEM) images and energy-dispersive
X-ray (EDX) mapping images were recorded to obtain the
interface information of Sn nanoparticles formed on the SnO2
catalysts. It can be seen that the distribution of Sn was wider
than that of O in the three catalysts aer the ECR test (Fig. 4a–c).
Additionally, clear lattice fringes with 0.334 nm and 0.279 nm
spacings corresponding to SnO2 (110) and Sn (101), respectively,
were observed in the high-resolution TEM (HRTEM) images
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taken from the surface regions of the three catalysts aer the
ECR test (Fig. 4d–f). Metallic Sn nanoparticles gradually formed
on the SnO2 NCs during the ECR.
We tracked the change in catalyst structure under different
potentials with reaction time using transmission electron
microscopy (TEM) to elucidate the relationship between the
formed Sn/SnO2 interfaces on the catalysts and their ECR
performances (Fig. 5). We focused on the Oct-{111} and Oct-
{221}, because even though their apparent morphologies are
similar, there were signicant differences in their ECR perfor-
mances (especially at low reduction potentials). The results
indicated that the construction of an effective Sn/SnO2 interface
was the key to ECR activity. At low potentials (
0.6 V vs. RHE),
no signicant changes were observed in the morphology of Oct-
{111} and Oct-{221} aer 1 h (Fig. 5a). However, some Sn
nanoparticles began to form on the surface of SnO2 NCs aer
2 h (Fig. 5b). In the subsequent reaction process, the octahedral
morphology of SnO2 NCs did not change signicantly, but the
formation of Sn nanoparticles showed different trends in Oct-
{111} and Oct-{221}. In the case of the Oct-{111}, the number of
Sn nanoparticles formed on the surface of the particles gradu-
ally increased, whilst the individual particles did not grow in
size. In other words, more and more Sn/SnO2 interfaces were
generated in the Oct-{221} as the ECR process went on. On the
other hand, in Oct-{221} the initially formed Sn nanoparticles
grew larger but their number didn't increase signicantly as the
reaction progressed. This differences in the number and size
evolution of the formed Sn nanoparticles between Oct-{111} and
Fig. 4 HADDF-STEM images and the corresponding elemental
mapping images of (a) Oct-{111}, (b) Oct-{221} and (c) Rod-{110} after
CO2RR tests; the corresponding HRTEM images of (d) Oct-{111}, (e)
Oct-{221}, and (f) Rod-{110} to show the interplanar lattice fringe
spacings.
Fig. 5 TEM images of Oct-{111} and Oct-{221} after ECR for different
times at potentials of (a and b)
0.6 V vs. RHE, (c and d)
0.8 V vs. RHE,
and (e and f)
1.0 V vs. RHE. The inset is the corresponding image at
a higher magnification (scale bar: 20 nm).
Oct-{221} indicate that the Sn/SnO2 interface is the actual active
site for ECR rather than Sn or SnO2, which may account for the
different FE–time variations of the products of the two catalysts.
This result is similar to previous reports.20,32 In fact, under the
potential of
0.8 V vs. RHE, the Sn/SnO2 interface could be
formed more rapidly on the surfaces of Oct-{111} and Oct-{221},
and the FEs of ECR products tend to achieve stability more
rapidly (Fig. 5c and d). When compared to Oct-{221}, Sn nano-
particles formed on the Oct-{111} had smaller size and were
more in number. This resulted in Oct-{111} exhibiting better
ECR activity. A similar relationship between the Sn/SnO2
interfaces and the FE of ECR products with time was also
observed in the ECR test under high potentials (
1.0 V vs. RHE)
(Fig. 5e and f). Thus, owing to the different stabilities in the
ECR, different types of Sn/SnO2 interfaces were established on
the {111} and {221} surfaces of the SnO2 catalysts, ultimately
leading to distinct ECR activities of the SnO2 catalysts and
selectivity of the products.
In order to further conrm the role of the Sn/SnO2 interface,
formed in situ in the ECR process, in the catalyst performance,
we compared the changes in the electrochemical surface area
(ECSA) and the interfacial charge transfer resistance (Rct) of the
three catalysts before and aer the reaction. The ECSAs of the
three catalysts were measured via double-layer capacitance tests
in CO2-saturated 0.5 M NaHCO3 solution. As shown in Fig. 6a,
the initial ECSAs of the three morphologically distinct SnO2 NCs
were similar. Aer a 6 hour reaction, the ECSAs of the three

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Fig. 6 (a) Charging current density differences plotted against scan
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rates. (b) Nyquist plots for Oct-{111}, Oct-{221} and Rod-{110}. Z0 and
-Z00 are the real impedance and imaginary impedance, respectively. EIS
measurements for the three samples were conducted under
a potential of
0.7 V versus RHE in CO2-saturated 0.5 M NaHCO3
aqueous solution.
samples increased signicantly. Typically, the ECSA of the Oct-
{111} aer the ECR test was approximately threefold larger than
that of the initial samples. Clearly, in situ formation of the Sn
nanoparticles during the ECR process roughens the surface of
the catalyst at different levels, thereby leading to an increase in
the catalytically active sites and improvement in catalytic
activity for CO2 reduction. The order of ECSAs of the three SnO2
samples aer ECR tests were Oct-{111} (slope: 1.87 mF cm
2,
area: 31.2 cm2) > Rod-{110} (slope: 1.61 mF cm
2, area: 26.8
cm2) > Oct-{221} (slope 1.47 mF cm
2, area 24.5 cm2), which was
consistent with the order of the catalytic activity for CO2
reduction.
The difference between the Sn/SnOx interfaces, formed in
situ on the three SnO2 samples, was also reected in the
changes in the interfacial charge transfer impedances before
and aer the ECR. Fig. 6b shows the electrochemical impedance
spectroscopy responses (Nyquist plots), in which the radius of
the semicircles represents the resistance (Rct) of interfacial
charge transfer. Aer the ECR tests, the Rct decreased, which
indicated that the formation of the Sn/SnOx interface was
conducive to the electron transfer. Among the three SnO2
samples, Rct of the Oct-{111} decreased the most aer the
reaction, indicating that the surface states of Oct-{111} catalysts
changed the most during the ECR process. This EIS result of the
Oct-{111} is consistent with the TEM images (Fig. 5). More and
smaller Sn domains are formed on the surface of the catalyst,
which means more creation of Sn/SnOx interfaces. Therefore,
the Oct-{111} aer the CO2RR has a smaller Rct than Rod-{110}
and Oct-{221}.33 Thus it was reasonable to assume that Oct-{111}
exhibited superior ECR performance as compared to Oct-{221}
and Rod-{110}.
On the basis of the results above, we propose that the Sn/
SnO2 interface is crucial for the ECR, and individual Sn or SnO2
may not be the real active site in ECR. Many previous studies
have revealed that the presence of SnOx in Sn-based electro-
catalysts can activate CO2 to CO$
2 and CO32
, which are
important intermediates for generating HCOO
.24–27 In the
absence of SnOx, Sn0 catalyzes only H2 evolution because the
electron transfer to CO2 is prohibitively slow.20 Removing the
surface oxide of the Sn-based catalysts will cause degradation of
the ECR performance.34 Furthermore, Seong Ihl Woo has found
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that the initial O content on the surface of the Sn electrodes
correlated with the formate selectivity in terms of the faradaic
efficiency.23 The heat-treated Sn dendrite electrode (i.e., 71.6%
for formate and 11.8% for CO) shows values 24.9 and 21.5
percentage points higher than the values for the Sn foil and Sn
dendrite electrodes, respectively. From the above Sn/SnOx
studies, it can be concluded that the absence of SnOx in Sn-
based electrocatalysts would lead to a worse catalytic activity.
In fact, the above studies also verify our opinion that the in situ
formation of a Sn/SnO2 interface on the surface of SnO2 cata-
lysts is the key factor for efficient ECR.
Conclusions
In summary, by using SnO2 NCs enclosed with well-dened
facets as the research reference, we probed the intrinsic rela-
tionship between the surface structure of SnO2 catalysts with
different exposed facets and their catalytic performances in the
ECR. Our experimental results showed that the in situ formation
of a Sn/SnO2 interface on the surface of SnO2 catalysts is the key
factor for efficient ECR. The ECR activity of the three SnO2
crystal planes followed the order {111} > {221}> {110}. Compared
to the other two samples, more Sn/SnO2 catalytic interfaces were
in situ constructed on the {111} surface in the ECR, thus
exhibiting better ECR activity and higher selectivity over {111}-
Oct for C1 products. This work reminds us that more attention
should be paid to the real surface states of the catalysts in the
catalysis process when we study the properties of catalysts in
ECR. This concept can be further extended to the design of
other oxide catalyst structures.
Experimental section
Chemicals
Hydrated stannic chloride (SnCl4$5H2O), hydrochloric acid
(HCl, 37.5%), poly(vinyl pyrrolidone) (PVP, K-30) and tetrame-
thylammonium hydroxide (TMAH) were purchased from Sino-
pharm Chemical Reagent Co. Ltd (Shanghai, China). All
reagents were used directly without any further purication.
Synthesis of octahedral SnO2 NCs enclosed by {221} facets and
rod-like SnO2 NCs dominated by {110} facets
In a typical synthesis of Oct-{221} SnO2 NCs, SnCl4$5H2O
(0.350 g, 1 mmol), HCl (0.60 mL), and PVP (0.315 g, 0.006 mmol)
were added in order to a mixed solution of ethanol and distilled
water (6.00 mL, 1/1 v/v) under intense ultrasonic treatment.
Then the resulting solution was transferred to a Teon-lined
stainless steel autoclave and maintained at 200  C for 12 h.
The products were collected by centrifugation at 4000 rpm, and
washed several times with deionized water and ethanol. The
rod-like SnO2 NCs (i.e., Rod-{110}) were synthesized in a similar
way except that 0.20 mL of HCl was used instead of 0.60 mL HCl.
Synthesis of octahedral SnO2 enclosed by {111} facets
In a typical synthesis, SnCl4$5H2O (0.350 g, 1.00 mmol) and
aqueous TMAH (17.00 mL) were successively added to ethanol
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(3.00 mL) under intense ultrasonic treatment. Then the result-
ing solution was transferred to a Teon lined stainless steel
autoclave (25 mL) and maintained at 200  C for 12 h. The
products were collected by centrifugation at 4000 rpm, and
washed several times with deionized water and ethanol.
Characterization of samples
The morphology and structure of the products were character-
ized by transmission electron microscopy (TEM, JEOL JEM-
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2100) at 200 kV accelerating voltage. High-resolution TEM
(HRTEM), high-angle annular dark-eld scanning TEM
(HAADF-STEM) and energy-dispersive X-ray (EDX) studies were
conducted on a TECNAI F-30 high-resolution transmission
electron microscope at 300 kV, and scanning electron micros-
copy (SEM, Hitachi S-4800) was performed at 10 kV accelerating
voltage. The compositions of the products were determined by
powder X-ray diffraction (XRD, PANalytical X'Pert).
Electrochemical measurements
All electrochemical properties were tested using a Princeton
4000+ with a three-electrode system at room temperature. The
as-loaded catalyst carbon paper served as the working electrode,
a platinum plate (1  1 cm2) served as the counter electrode,
and a Ag/AgCl (saturated KCl) electrode served as the reference
electrode in 0.5 M NaHCO3 aqueous electrolyte (pH 7.2). For
preparation of the working electrode, 1 mg catalyst was added
into 200 mL ethanol and then sonicated for 30 min. 200 mL of
catalyst suspension was dropped on carbon paper with
a geometric area of 1  1 cm2. Linear sweep voltammetry (LSV)
and chronoamperometry were both performed in an H-type
electrolytic cell, where the cathode and anode compartments
were separated by Naon-115 membrane. Each half-cell
contains 25 mL electrolyte with a gas headspace of 5 mL.
Before testing, the electrolyte was purged with CO2 or N2 for
least 30 min with a ow rate of 10 mL min
1. During the
chronoamperometry measurements, the gas products were
analyzed using a TCD (thermal conductivity detector) for H2 and
an FID (ame ionization detector) for CO and hydrocarbons.
The gas products were tested every 10 min. A gas chromato-
graph (GC-2014C, Shimadzu) equipped with PLOT Mol Sieve 5A
and Q-bond PLOT columns was used for quantications. Ar
(99.999%) was used as the carrier gas. Liquid products were
analyzed using 1H NMR spectra, which were recorded on an
Advance III 500 MHz Unity Plus spectrometer (Bruker), in which
0.4 mL of the electrolyte was mixed with 0.1 mL of D2O
(deuterated water), and 0.1 mL of dimethyl sulfoxide (DMSO)
(99.99%, Sigma) was added as an internal standard. The
Nyquist plots were measured with frequencies ranging from 100
kHz to 0.1 Hz, and the amplitude of the applied voltage was
1 mV. The impedance data were tted to a simplied Randles
circuit to extract the charge-transfer resistances. The electro-
chemically active surface area (ECSA) was determined by
measuring the capacitive current associated with double-layer
(Cdl) charging from the scan-rate dependence of CVs (the
potential window was
0.25 V to
0.35 V versus Ag/AgCl). Cdl
was estimated by plotting the current density (Dj) at
0.3 V
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versus Ag/AgCl (0.5 M NaHCO3 solution). The Nyquist plots,
showing electrochemical impedance spectroscopy (EIS)
responses, were measured with frequencies ranging from 100
kHz to 0.01 Hz, and the amplitude of the applied voltage was
5 mV.
Conflicts of interest
There are no conicts to declare.
Acknowledgements
This work was supported by the National Key Research and
Development Program of China (2017YFA0206500 and
2017YFA0206801), the National Basic Research Program of
China (2015CB932301), and the National Natural Science
Foundation of China (21671163, 21721001, 21773190, and
21931009). Jianyang Wu is grateful for the support of NFFTBS
(No. J1310024).
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