Khu CO2 Cheng 2020

Recent progress of Sn-based derivative catalysts for electrochemical reduction of CO2
Feng Chenga, b, #, Xinxin Zhangb, c, #, Kaiwen Mub, c, Xin Mab, Mingyang Jiaob, Zhiheng Wangb, c,
Paphada Limpachanangkuld, Benjapon Chalermsinsuwand, Ying Gaoa, Yunhui Lia, *, Zhipeng Chenb,
*
, Licheng Liub, e, f, *
a
Changchun University of Science and Technology, Changchun, Jilin, 130022, China
Accepted Article
b
CAS Key Laboratory of Bio
Bio-based Materials, Qingdao Institute of Bioenergy and Bioprocess
Technology, Chinese Academy of Sciences, Qingdao, Shandong, 266000, China
c
University of Chinese Academy of Sciences, Beijing 100049, China
d
Department of Chemical Technology, Faculty of Science, Chulalongkorn Univers
University, 254
Phayathai Road, Wangmai, Pathumwan, Bangkok 10330, Thailand
e
Dalian National Laboratory for Clean Energy, Dalian, Liaoning, 116023, China
f
Key Laboratory of Biomass Chemical Engineering of Ministry of Education, Zhejiang University,
Hangzhou 310027, China
#
These authors contributed equally to this study.
E-mail:
liyh@cust.edu.cn liulc@qibebt.ac.cn
Keywords: carbon dioxide, electrochemica

electrochemical reduction, Sn-based catalyst, electrocatalysis
Abstract
Using renewable electric power to drive CO2 electrochemical reduction to high value-added
chemical fuels can not only solve the excessive emission of CO2, but also achieve the direct
conversion of intermittent electrical energy to chemical energy, which is of great significance for
controlling carbon balance and optimizing energy consumption structure. In recent years, various
kinds of electrocatalysts have been used in the research of CO2 electrochemical reduction reaction
(CO2RR) and some progress has been made in the key scientific issues such as improving
selectivity and reducing overpotential of reactions. Owing to the low cost, environmental
friendliness and high selectivity to formic acid, Sn-based catalysts are most likely to be applied in
This article has been accepted for publication and undergone full peer review but has not
been through the copyediting, typesetting, pagination and proofreading process, which may
lead to differences between this version and the Version of Record. Please cite this article as
doi: 10.1002/ente.202000799.
This article is protected by copyright. All rights reserved

the CO2RR field on a large scale. In this review, the research progress of Sn-based catalysts,
including the research status of metallic tin catalysts, Sn-based oxides, oxide-derived tin catalysts,
Sn-based sulfides, and the four strategies used commonly to improve efficiency and selectivity are
systematically summarized and discussed. Additionally, the major challenges and several
Accepted Article
perspectives on the further research directions of Sn
Sn-based catalysts for CO2RR are proposed.

1. Introduction
With the development of industry and the improvement of living standards, carbon dioxide
emissions have increased significantly year by year, causing serious environmental problems, such
as the global warming and climate change, which have been receiving much attention.[1] Effective
Accepted Article
capture and utilization of carbon dioxide is an important means to alleviate the increase in carbon
atmosphere.[2]
dioxide content in the atmosphere
The electrochemical reduction reaction of carbon dioxi

dioxide (CO2RR) can not only effectively
solve the problem of environmental impact brought by the excessive carbon dioxide emissions, but
also convert unstable renewable resources to stable chemical energy for storage. [3] Therefore, the
target of recent research is how to transfer carbon dioxide into valuable chemicals and fuels. [4]
Among these high-

high-value-added
high -value
value-- chemical substances, formic acid is one of the most widely range of
application as reactant materials in the dye and leather industry.[5] Moreover, formic acid can also
be treated as one of the centers of energy transportation and preservation, that is, simple and
effective conversion into H2 or CO.[6] Compared with other possible chemical product conversion
pathways, the reduction process of CO2 to C1 products (CO and formic acid) is a classic double
electron transfer reaction that easily occur

occurs, and the electron utilization efficiency is very high.
Therefore, it is considered to be an economically feasible, simple and effective method.[7]
Due to the thermodynamic stability of carbon dioxide molecules, the reduction process is
difficult to complete spontaneously. The participation of the catalyst can shorten the time required
for the reaction to reach equilibrium. By adjusting the structure of the catalyst, the occurrence of
hydrogen release reaction (HER) can also be effectively reduced, and the selectivity of the
reduction product can be effectively controlled. To a large extent, the development of CO 2RR
mainly depends on the design of high-performance and robust electrocatalysts. Although the nano-
structured noble metals, such as gold (Au),[8] silver (Ag)[9] and palladium (Pd)[10] exhibit excellent
catalytic activity and high selectivity for C1 products,[11] the use of these noble metals in large-

scale or industrial production is limited due to the high cost. Therefore, it is a prominent problem in
the development process to study electrocatalysts with lower cost, better performance and higher
product selectivity.
Focusing on the research field of non-noble metal catalysts, owing to its excellent catalytic
Accepted Article
performance, tin- based catalysts have attracted much attention in the electrocatalytic of CO2RR.[12]
tin-based
tin -based
Firstly, tin metal and its compounds have high selectivity to formic acid products in tthe catalytic
process, which is conducive to the separation and purification of chemical products. Secondly, tin
non-toxic, suitable for large-scale apply.[13] In the field of electrocatalysis, the

metal is abundant and non
size,[1a, 14] morphology[[15

[15]
15]]
and structure[16] of Sn-based catalysts have a great impact on its catalytic
performance. This article reviews the research progress of Sn

Sn-based catalysts, including the
Sn-based oxides,[15b, 16b, 16c, 17] oxide-derived tin catalysts,[12]

research status of metallic tin catalysts, Sn
Sn-based
based sulfides, and the four strategies used commonly to improve efficiency and selectivity are
systematically summarized and discussed. In addition, the major challenges and several
perspectives on the further research direct

directions of Sn-based catalysts for CO2RR are proposed.
2. Mechanism
echanism of Sn-
Sn-based
Sn -based
based catalysts for CO2RR
2.1 Fundamental for CO2RR
In the laboratory research phase, CO2RR is usually carried out in a double-chamber H-type
electrolytic cell with good airtightness, which is composed of the three parts, including cathode
chamber, anode chamber and ion

ion-exchange membrane. Among them, the cathode chamber consists
of working electrode (mainly by the catalyst coated on carbon cloth or other conductive carrier)
ectrode and the anode chamber consists of counter electrode (mostly platinum).[18] As
reference electrode
explained by a hypothetical mechanism, carbon dioxide molecules in the electrolyte diffuse to the
surface of the working electrode during the reduction process, a single electron combined with
carbon dioxide molecule, and producing a CO2•− radicalanion.[19] However, carbon dioxide
molecules are thermodynamically stable. The bonding energy of C=O bonds is 750 kJ mol -1, which

requires a lot of energy to destroy its molecular structure.[20] Therefore, a higher reduction potential
(i.e., -1.9 V vs. NHE) is required in this process.[21]
In addition, due to the similar reduction potential, the occurrence of CO2RR in the cathode
chamber will also be accompanied by the generation of hydrogen evolution reaction.[21-22] Moreover,
Accepted Article
under standard conditions ((101.325 KPa, 273 K), the process of the electrolysis of H2O demands
237.2 kJ mol−−11 of energy, CO2 reduction to hydrocarbon fuels CH4 and CH3OH requires 818.3 kJ
mol−1 and 702 kJ mol−−11, respectively. Therefore, the activation of H2O is much easier than CO2 and
even forms a competitive relationship with CO2 activation process.[18] As shown in Table 1,
through different reaction pathways, a large number of carbon products were generated, including
multi-carbon products (CH3OH, C2H4...).[23] With the participation of H+, the

HCOOH, CO, and multi
redox potential required for the reduction of CO2 to CO, HCOOH and other products is much lower
than that for the formation of CO2•− free radical anion.[1d, 22] All these factors make CO2RR suffered
from ann enormous challenge.[20, 24] Therefore, the emergence of high-efficiency catalysts is the key
to solving the problems in CO2RR.
As shown in Fi
Figure
gure 11, it is generally believed that CO2RR involves two reaction pathways.
Pathway Ⅰ, first, the oxygen atoms in *CO2•− are bound to the surface of catalysts, and then, under
the protonation of carbon atoms, *CO2•− is reduced to *OCHO (the intermediate of formic acid).
Finally, HCOOH is formed and desorbed from the catalyst surface. Additionally, *OCHO can be
reduced to biformate (*H2COO) to compete with the formation of HCOOH. Pathway Ⅱ, first, the
carbon atoms in *CO2•− are combined with the catalyst surface, and then, under the protonation of
oxygen atoms, the *CO2•− is reduced to *COOH (carboxylate intermediate). Finally, CO is formed
and desorbed from the catalyst surface. And *COOH can also be reduced to HCOOH to compete
with CO. In addition, both *H2COO and *CO are generally regarded as intermediates in the multi-
proton/electron reaction pathway, resulting in the formation of multi-carbon products such as
CH3OH and C2H4.

The catalyst evaluation mechanism for CO2RR consists of many factors and reference
standards， among which the common key parameters include current density, overpotential,
faradaic efficiency, turnover frequency, etc.[18]
(1)) Current density ((j

(j)
j)
Accepted Article
In electrochemistry, a corresponding electrolysis current (i) is generated under the action of a
constant voltage, and the electric current passing through the geometric surface area of working
electrode (A)) is defined as current density ((j).
�
𝑗=� (1)
(2) Overpotential ((𝜂

(𝜂)
𝜂))
Overpotential is the differential value between the actual required potential for the reaction to
proceed at a rate and the minimum theoretical calculated potential by thermodynamically.[25] In the
process of CO2RR, overpotentials mainly comes from the activation energy needed by single
electron transfer to carbon dioxide molecule, electric quant

quantity loss and mass transport loss
required.[26] This parameter (𝜂) represents the additional driving force required to drive a reaction
at a specific rate.
𝜂 = 𝐸 − 𝐸�� (2)
(3) Faradaic Efficiency (FE

((FE)
FE
Faradaic efficiency is the specific value of actually electric charge to the theoretically electric
charge generated by the total products. Among them, theoretically electric charge was the product
of the number of electrons transferred ((α), the amount of desired product’s moles (N), and the
F,, 96485 C mol−1).

faradaic constant ((F
(F,
F
��
𝐹𝐸 = (3)
�
(4) Turnover Frequency (TOF)
Turnover Frequency is related to the quantity of carbon dioxide transformation products and the
increased number of active sites per unit time. The more active sites the catalyst fixed, the higher
the turnover frequency and the better the catalytic activity. It is the ratio of the target product per
unit time (𝑁� ) and the maximum number of moles of the catalyst active site (𝑁� ).[27]
��
𝑇𝑂𝐹 = (4)
��
2.2 Mechanism research progress of Sn

Sn-based catalysts
Accepted Article
Although some progre
progress has been made in the study of Sn-based catalysts, the deeper reaction
mechanism remains to be revealed. The lack of deep insight into the reaction mechanisms and clear
identification of the origin for catalytic activity hinder breakthrough in the develo
development of high
performance and durability electrocatalysts. As far as current research methods are concerned, in
situ/operando characterization techniques combined with density functional theory ((DFT)
theoretical calculation is the most effective method to reveal the reaction mechanism.
2.2.1 Operando characterization techniques
Operando characterization techniques, which can in situ monitor the surface oxidation state
and local atomic structure transition, can probe the active sites and promote the fundamental
understanding of the reaction mechanism. The structure and activity of electrocatalyst were
connected with the

the chemical nature and population of interfacial species, providing the foundation
of the interfacial spectral characterization or evaluation.[28]
The electrode/electrolyte interface reaction is a core part of the CO2RR, which needs
synergistic effect betw

between
een the in
in-situ microscopic and spectroscopic techniques. Due to the easier to
operate, lower features cost and more widely applicability, the surface IR spectroscopy have
received intensive attention.[29] Surface IR spectroscopy with either external reflection (IRAS or
IRRAS) or internal reflection (ATR

(ATR-IR or ATR-FTIR) was commonly used. Bocarsly et
al.[30] utilized the in-situ ATR-IR to explore the CO2RR on the mixed Sn/SnOx thin films electrode,
which were deposited onto a single-crystal ZnSe ATR crystal. And they proposed a mechanism
governing CO2RR on tin electrodes through a series of experiments. In-situ ATR-IR spectroscopy
demonstrates that the surface-bound tin-carbonate species caused the strong vibrational stretches

under the process of CO2 reduction. If the process was prevented by the change of the reaction
conditions, the vibrational stretches were dramatically decreased or disappear. Therefore, the
conclusion was drawn, the Sn carbonate species that combined in the surface is an active
intermediate in the CO2RR. Zheng et al.[31] designed a two-dimension ultrathin Pd nanosheets

Accepted Article
structure, which was modified by SnO2 nanoparticles. According to a much stronger absorption at
2350 cm-1 for the Pd/SnO2 by the in situ diffuse reflectance infrared Fourier transform (DRIFT)
spectroscopy data, indicating the enhance of adsorption for CO2 in the Pd-SnO2 interface and the
weak binding for CO, which was beneficial to enhance the electrocatalytic selectivity and stability
for Pd catalysts. Although in

in-situ infrared spectroscopy technique has been applied to explore the
reaction mechanism of tin

tin-based catalysts, the current in-situ characterization techniques still need
to be explored.
red. Other advanced operando characterization techniques should be encouraged, such as
in situ XPS, XAS and Raman.
2.2.2 DFT calculation
Density functional theory ((DFT) calculation is a quantum mechanical method used to research
the electronic structure of multielectron systems, which is widely used in physics and chemistry,
especially in the study of the properties of molecules and condensed matter. In the field of
electrocatalysis
ctrocatalysis research, DFT calculation is one of the effective auxiliary methods for mechanism
research, which can predict the activity and directionality of the electrocatalytic reaction according
to the electronic structure of the catalysts.
There is an inevitable connection between the inherent electronic structure and physical
properties of the electrocatalyst for CO2RR with the catalytic performance and target product
directionality.[32] The Sn-based oxides with the various electronic structures stand a good chance of
the different adsorption and activation behaviors for CO2 and intermediates.[32c] For example, Luo
et al.[33] used the DFT calculations to research the process of the CO2 to HCOOH conversion,
including the changes of electronic energies and free energy, and the interaction between

electrocatalysts and intermediates. Such as the SnO2 catalysts, there were two adsorption sites (O
atom and Sn atom) (Figure 2a). As shown in Figure 2b, the electron energy and geometric
configuration of the intermediates at different adsorption sites were determined. It can be concluded
that the first step of the CO2RR pathway was the competitive adsorption of the intermediates
Accepted Article
*OCHO and *COOH on the catalyst surface, and Sn4+ in SnO2 was confirmed as the active site of
CO2RR by adsorption energy allocation and Gibbs free energy calculation results, and the presence
of Sn4+ can effectively reduce the overpotential of CO2 reduction.[34] Figure 2c shown that the first
step was protonation process in which hydrog

hydrogen ions and electrons were combined with CO2 on the
surface of the catalyst to form *OCHO intermediate. The second step is hydrogenation of *OCHO
to form *HCOOH, and the third step is desorption of *HCOOH from electrocatalyst surface.
According to the energy

energy barrier to be overcome as needed, the rate
rate-determining step (RDS) on SnO
was the process of HCOO* formation, apart from this, the process of HCOO* hydrogenation to
form *HCOOH was the RDS for SnO2 and Sn3O4. Liu et al.[35] explored the effect of amino-
functionalized
unctionalized carbon layer on the catalytic activity of SnS from the perspective of the difference in
adsorption energy caused by the change of electronic structure. According to DFT calculations, the
free energy to form OCHO* intermediate was significantl

significantly decreased after combining with amino-
functionalized carbon layer ((Figure 2d), which leads to a significant increase in catalytic selectivity
of formic acid. They further calculated the adsorption energies of reaction intermediates on the
surface.. As shown in Figure 2e-f, the SnS/Aminated-C composite catalyst demonstrates

catalyst surface
higher adsorption energies of CO2*, OCHO*, and COOH* intermediates and lower adsorption
energies of CO* intermediate than that of unmodified SnS catalyst, suggesting that the bonding
strength of the catalyst to the OCHO* intermediate was stronger and the CO was easier to desorb
from the catalyst surface, which break the conventional scaling relations of reaction intermediates.
Furthermore, they explained the difference in adsorption energy from the change in electronic
structure of catalysts. Differential charge calculation result revealed that the charge on the adjacent

N atoms were transferred to the surface of Sn atom (Figure 2g). The redistribution of charge
enhanced the electron mobility and the charge transfer rate, resulting in the change of adsorption
energy.
So far, the systematic theoretical modeling and experimental verification are still insufficient
Accepted Article
in terms of structure-
structure-performance
structure-performance
performance for the catalysts. Advanced theo
theoretical calculations can not only
reveal the reaction mechanism, but also help to down

down-select efficient catalysts and guide the
synthesis of catalysts. However, the catalyst model is oversimplified in some DFT calculations for
CO2RR, which leads to a diffe

difference between the real structure of the catalyst and the theoretical
model. Therefore, the DFT calculated results were not rigorous. Thus, we should pay close attention
to whether the DFT model truly corresponds to the real structure of the catalyst in the future
researches.
3. Sn-based
based catalysts for CO2 electroreduction
3.1
.1 Metallic Sn catalysts
With low cost and high formic acid selectivity, the metallic Sn is an environmental
environmental-friendly
catalyst in electro-
electro-catalytic
electro -catalytic reduction of CO2. Numerous metallic Sn catalysts have been deeply
investigated, but they have many problems such as the large overpotential, low faradaic efficiency
reaction.[36]
for the competitive hydrogen evolution reaction
Several me
metallic
m etallic Sn-based catalysts are briefly listed.[15c,
tallic Sn 37]
Janáky et al.[38] studied the
electrocatalytic behavior of different intermetallic phases toward CO2RR of Au-Sn bimetal
(Figure 3a). The reasonable intermetallic phase demonstrated the lowest

nanoparticles (Figure
overpotential for CO2 reduction. Unde

Under the optimal conditions, the highest current density of formic
acid and simultaneous syngas in the gas could be obtained. Chen et al.[39] reported a Pd-Sn alloy
electrocatalyst that displayed extremely high faradaic efficiency of HCOOH at -0.26 V (Figure 3b-
d), completely inhibiting the production of CO and hydrogen. Zeng et al. [40] applied a simple
electrodeposition process to produce a modified porous copper foam Cu-Sn catalyst with three-

dimensional porous dendrite architecture (Figure 3e-f), which achieves a maximum FECO of 94%,
and a high partial current density of 7.9 mA cm-2 at applied potential of -1.1 V (vs. RHE).
Bond et al.[41] produced a new type of metal electrocatalytic material. On the basis of platinum,
copper, tin and indium substrates, the variety of Sn-based catalyst with dendritic structure were
Accepted Article
adopted by hydrogen bubble assisted electrodeposition. with a different bond length in average
between the coated metal atoms and the variety substrates, the strain effect changes the number of
electronic and the chemical natures of the catalyst surface, which can improve the catalytic
performance. Among them, the dendritic Sn/Cu catalyst has the highest selectivity to formic acid,
as shown in Figure 33g h.. In the comparative experiment carried out by Wang et al.,[42] it was found
3g-h.
g--h
that the optimal deposition current density of Sn electrode is 15 mA cm-2 at -1.4 V (vs. SCE). Under
this condition, the efficiency of CO2 conversion exceeds 91%. It can be seen that the dominant
strategy for the improvement of the catalytic performance of Sn

Sn-based catalysts is to promote
electron transport by introducing conductive materials.
3.2 Oxide-derived
derived Sn catalysts
Under electroche
electrochemical
mical oxidation treatment or natural oxidation, oxide derived tin appears on
the surface of metal tin electrode.[43] Oxide derived Sn catalysts also have good catalytic
performance. For example, Meyer et al.[1a] prepared Sn oxide supported graphene nanocatalysts by
hydrothermal method, which has a higher surface area, as shown in Figure 4a-b. CO2 can be
reduced to formic acid under lower over

over-potential conditions. At -2.0 V (vs. SCE), current density is
higher than 10 mA cm--22, and the faradaic efficiency of the product is greater than 93%. Due to the
electronic interaction between the graphene layers, the protonation between metal Sn and CO 2
promotes the improvement of the catalyst performance.
With simple hydrothermal process, Qiao et al.[44] obtained a multiwalled carbon nanotubes
layered structure loaded with SnOx nanosheets by simple hydrothermal process, and the selectivity
of C1 products was furtherly improved by the functionalization of -COOH, -NH2 and -OH groups

(Figure 4c-d). The interaction of Sn and functional groups also have a positive effects to
electrocatalytic performance. Similarly, the interaction between metals and oxides can also
effectively enhance the electrocatalytic performance of catalysts.[45] Huo et al.[46] reported that the
electrochemical performance of the Cu/SnOx hetero structured nanoparticles coated on carbon

Accepted Article
nanotubes (CNTs). The CO FE for the 30.2% SnOx catalyst up to 77%, and a current density of 4.0
mA cm-2 at --0.99
0.99 V (vs.
(vs. RHE), which was higher than SnOx-CNT catalysts that converts CO2 to
HCOOH in FE of 48% (Figure 4e-f).
The natural Sn-

Sn-oxide
Sn -oxide
oxide layer on the surface of the Sn electrode can promote the performance of
the catalyst. For example, Kanan et al.[47] evaluated the influences of tin oxide (SnOx) layer on CO2
reduction efficiency. As a result, the electrodeposited SnOx catalyst exhibited higher current density
and higher FE than that of natural SnOx catalyst (Figure 4g-h). The thickness of the oxide layer
electrocatalytic activity of the Sn catalysts. Zhou et al.[48]

also has a certain influence on the electrocat
confirmed that the thickness of SnOx layer (100 nm) on the Sn nanoparticles has little effect on
current density, but it is closely related to the selectivity of products ((Figure 4i-j). The thinner
natural SnOx layer exhibits higher formic acid selectivity. As the thickness of SnOx layer increased,
the yield of H2 was much higher than that of HCOOH, and the faradaic efficiency of hydrogen also
increased significantly. In order to obtain the target pr

product formic acid, the hydrogen production
needs to be inhibited, indicating that the optimal SnOx layer thickness needs to be explored. By
self-assembly and accommodation, Qiao et al.[49] synthesized tin-based

using a facile hydrothermal self
oxide composite w
with
ith a coral wire structure. The catalyst displayed good durability and stability in
catalytic applications, with a stable catalytic current density of 10 mA cm-2 with over 20 h
electro-catalytic
of continuous operation.
3.3 Sn-based oxides
3.3.1 SnO
A series of studies have proved that, Sn-based oxide catalysts exhibit higher specific surface

area and higher roughness, which were more conducive to the adsorption of CO2 molecules.[31] Tin
element mainly has two valence states of +2 and +4 in its metal oxide. Compared with SnO2, SnO
nanoparticles, usually demonstrate a higher current density and product selectivity.[50] For example,
in 2017, Hu et al.[23c] synthesized SnO anoparticles with ultra-small size (~2.6 nm) and applied
Accepted Article
them to CO2RR with good catalytic performance. In the potential range of -0.5 to -0.9 V (vs. RHE),
the total faradaic efficiency of the C1 products gradually increases, and it can reach about 95% at -
0.9 V. In 2019, Guan et al.[5] prepared Bi-doped SnO nanosheets grown on Cu foam-based materials
by hydrothermal synthesis. The highest faradaic efficiency of formic acid reaches 93% with a
current density of 12 mA cm-2 at -1.7 V (vs. Ag/AgCl). The mechanism research proves that doping
of Bi element can maintain the stable existence oof a large amount of divalent tin (Sn2+) on the
surface of the catalyst, and it is not easy to be reduced to metallic tin (Sn). In this catalyst, Bi
doping improves the selectivity of the product, and the use of Cu foam
foam-based materials also has an
influence on enhancing the adsorption of *OOCH intermediates.
3.3.2 SnO2
Recently, different forms of SnO2 nanostructures have been widely reported, including SnO2
hollow structures,[[5
[51]
51
1]]
nanoparticles,[52] nanosheets,[53] nanowires,[54] nanorods and layered
structures.[52]] The synthesis method is relatively simple, mainly involving the polyol method,
thermal evaporation method, hydrothermal method, solvothermal method, etc.[55]
In order to further increase the number of active sites of the catalyst and the contact area with
CO2 molecules, a hollow linear tubular structure was obtained through the fusion with the hollow
structure on the basis of linear structure. Li et al.[54a] synthesized one-dimensional SnO2 with wire-
in-tube architectures using simple and low-cost electrospinning technology. The as-prepared hollow
nanowire structure has a high specific surface area and an amount of grain boundaries, as shown in
Figure 5a-b, effectively improving the catalytic performance. Figure 5c shows that the faradaic
efficiency of C1 product is over 90% in the potential range of -0.89 V to -1.29 V (vs. RHE). In 2020,

Zhang et al.[54b] prepared a SnO2-coated nitrogen-doped carbon nanowire three-dimensional
electrocatalyst (SnO2@N-CNW) by hydrothermal synthesis (Figure 5d-e). SnO2 is uniformly
dispersed on one-dimensional nanowires and has a high coverage rate. It can form an unique high-
density tin oxide layer, and a three-dimensional structure catalyst with rich pore structure. Owing to
Accepted Article
the aggregation of nanoparticles into large particles, the problem of reduced activity was effectively
solvothermal conditions using a SnS2 precursor, Wang et al.[53b]

avoided. Under low temperature solvot
first applied a two-

two-step
two -step
step strategy to synthesize a porous SnO2 nanosheet with a loose structure
(Figure 5f-g).
). This porous nanosheet is a non
non-aggregated and stable high-surface area nanostructure,
and
nd its unique structure is conducive to the improvement of electrochemical performance.
Grain boundaries can effectively enhance the number of active sites in the process of CO2
reduction and obtain valuable reduction products.[56] In the local space near the boundary of the
grain boundaries, the destruction of symmetry can adjust the binding energy of the reaction
intermediate and promote the reduction process.[57] In Sn-based catalysts, it can increase the
selectivity of formic acid

acid products. It was confirmed that, from the experiments performed by
Spurgeon et al.[[5
[54c]
544c]
c]
SnO2 porous nanowire catalysts have high grain boundary density and energy
conversion efficiency than other SnOx catalysts. The initial potential for the formic acid formation
is relatively low (350 mV), the faradaic efficiency of HCOOH reaches 80% at -0.8 V (vs. RHE).
Mechanism research shows that tthe high density of grain boundaries in the pores provides more
catalytically active sites, which is beneficial to the im

improvement of catalytic performance. The
improved catalytic performance of Sn oxides is dominantly due to the enhanced electron transport
capability and the increased surface area of the catalyst this includes increasing the grain boundary
density of the catalyst.
3.4 Sn-based sulfide
In the study of CO2RR, Sn-based oxides are widely used catalysts in their derivatives.
Additionally, other Sn-based derivatives, such as sulfides, also illustrate excellent catalytic

performance. Zeng et al.[58] prepared ultra-thin SnS2 nanosheets modified by Ni atoms through
element doping engineering. This thin atomic layer catalyst can effectively reduce CO 2 to formate,
achieving a largest current density of 19.6 mA cm-2 at -0.9 V (vs. RHE), and the faradaic efficiency
of the carbon product is stably maintained at 90%. The improvement of catalytic performance is
Accepted Article
mainly due to the increase in the defect level of Ni doping, which lead to a decrease in the work
function. Sargent et al.[[59

[59]
59
synthesized Sn(S)/Au catalyst with simple SnSx atomic layer deposition
method. The composite catalyst with higher oxidation state demonstrates a current density of 55
mA cm-2 with the faradaic efficiency of 93%. In addition, In addition, compounding with the
functional groups modified carb

carbon materials can also significantly enhance catalytic activity of Sn-
based sulfide catalysts. Zhang et al.[60] applied hydrothermal synthesis to prepare SnS2 nanosheets
loaded with reduced graphene oxide (SnS2/rGO), which shows a high selectivity to HCOOH at low
potential. And the highest faradaic efficiency of HCOOH is up to 84.5% at -0.68 V (vs. RHE). SnS2
in the reduction process effectively stabilizes the intermediate (CO2•−) and enhances the stability of
he catalyst. In 2020, Liu et al.[35] reported a hollow nanorod that was formed by amino-
the
functionalized carbon-
carbon-modified
carbon -modified
modified SnS nanosheets. After the amino-modification, the current density
and formic acid productivity of SnS catalysts were remarkably enhanced. Demonstrating the
highest faradaic efficiency of formic acid of 92.6% and a largest formate partial current density of
41.1 mA cm--22 at --0.9

0.9 V ((vs. RHE) with good stability. DFT calculations demonstrate that the
increased activity is owed to the synergisti

synergistic effect among SnS and amino-functionalized carbon
coating in increasing the adsorption energies of OCHO* intermediates. The morphology, crystal
defects, elemental dopants, and electronic structure of the Sn

Sn-based sulfides catalysts all played a
key role in the increase of product selectivity.
As shown in Table 2, we summarize the activity of various Sn-based catalysts reported for
electrochemical CO2RR to formic acid in recent years. It can be clearly seen that conductive matrix
or metal doping has a good performance in improving Sn-based catalysts activity of CO2RR, the

morphology and size of the catalyst also have a significant influence on the catalytic activity of
CO2RR. In addition, Sn-based sulfide catalysts generally exhibit a greater current density for
CO2RR than Sn-based oxide or metallic Sn catalysts.
4. Strategies for improving efficiency and selectivity

Accepted Article
4.1
.1 Morphology effects
The shape of the nano

nano-catalyst has a certain influence on the catalytic activity. Recently, a
large number of different forms of nano-catalysts have been reported, such as hollow structures,[78]
nanowires,[66]
66]]
nanoparticles,[60] layered structures,[65] embedded structures, etc. Among them, the
nanowire structure has a large specific surface area, and the synthesis method is mainly a simple
hydrothermal method. Li et al.[54a] synthesized SnO2 with wire-in-tube architectures using simple
cost electrospinning technology. Sun et al.[55e] prepared branched and sub-branched SnO2
and low-cost
hierarchical architectures
architectures by a multistep thermal vapor deposition route. The numerous aligned
SnO2 nanowires grew on the surface of the nanobelt substrates. These nanowires effectively
increase the specific surface area of the catalyst, which is conducive to the expansion of CO2
contact area. Among them, the empty structure can be used as a charge transmission channel, which
is also conducive to a large amount of CO2 adsorption and produce a positive effect on the
improvement of charge density and catalytic activity.
Compared with the nanowire catalyst, the nanosheet has stable structure, which can maintain a
good morphology and promote the electrocatalytic reaction. The stable planar structure increases
the active area that participates the reaction in two

two-dimensional space with stable structure. The
stable structure, loose porosity, high specific surface area and ultra
ultra-thin characteristics all have a
positive influence on the improvement of catalytic active sites. Zhang et al.[52] reported that,
obtained by loading mesoporous SnO2 nanosheets on carbon cloth, the three-dimensional layered
nanocatalysts produced high selectivity for formic acid. Wang et al.[53b] first implemented a two-
step strategy to synthesize a porous SnO2 nanosheet with a loose structure under low temperature

solvothermal conditions using a SnS2 precursor. The multi-dimensional structure can effectively
reduce the aggregation of nanoparticles, and obviously improve the problem of low activity caused
by agglomeration.
The mesoporous or hollow structure provides a channel for electron transfer and CO2
Accepted Article
transmission, which can cooperate in the CO2 reduction process to reduce the overpotential and
increase the energy transfer efficiency. Zhao et al.[79] prepared Sn/SnO2 porous hollow fibers
utilizing a facile
facile combination of electrospinning and reduction process. The catalyst shows high
selectivity for HCOOH, and long

long-term stability. This partial reduction reaction can artificially
control the Sn electronic structure and produce a large number of oxygen vac
vacancies, thus improving
the catalytic.
Li et al.[[5
[53c]
533c]
c]
prepared mesoporous SnO2 nanosheet catalysts by utilizing the self-template
Figure 66a
method (Figure 6a-b).
a--b
b).
). Figure 6c indicates that the highest faradaic efficiency of formic acid of
83% is obtained at around -0.7 V (vs. Ag/AgCl). In short, the catalyst has a low initial potential, a
large current density, and a high selectivity to formic acid. Zhang et al.[52] reported that the three-
dimensional layered nanocatalysts

nanocatalysts obtained by loading mesoporous SnO2 nanosheets on carbon
cloth (Figure 66d

6d-e).
d--ee).
). When the applied potential is -1.6 V (vs. Ag/AgCl), the faradaic efficiency of
formate is up to 87%, and the current density is 45 mA cm-2 (Figure 6f). From a series of
comparative experiments, it is concluded that the rich porous layered structure of the nanosheets
provides a larger specific surface area, promotes the transfer of charge, and enhances the
electrocatalytic performance.
In Figure 77a
7a-b,
a--b Zheng et al.[51] prepared the different mesoporous SnO2 catalysts with
b,, Zh
distinctive mesopore sizes and structures by the different surfactants (Figure 6a-b). It was found
that the total faradaic efficiency of the C1 product (CO and HCOOH) climbs to 80%, and the
current density is 5 mA cm-2 when the potential reaches -0.8 V (vs. RHE) (Figure 7c). Due to the
special hollow structure, it provides oxygen vacancy defects, effectively promoting the adsorption

of CO2 molecules. The mesoporous structure provides a channel for electron transport, effectively
reducing the overpotential. The synergistic effects of the two aspects ultimately promote the
catalytic performance of electrocatalyst. Qi et al.[78] used mesoporous silica as a template to prepare
SnO2 nanotubes. Amal et al.[66] adopted a simple nano-casting method for the first time to
Accepted Article
synthesize hollow SnO2 fiber catalyst (Figure 7d-e). The main product obtained in CO2RR is
HCOOH.. When the applied potential is -1.15 V (vs. RHE), the faradaic efficiency of formic acid is
up to 75%, and the current density is 10.8 mA cm-2 (Figure 7g). The contact area of the CO2
molecule of the hollow-

hollow-structured
hollow -structured
structured nano
nano-catalyst increases by multiples, which is more conducive to
the reaction.
Doping with heterogeneous atoms is one of the effective ways to further enhance the activity
based oxides catalysts. Zheng et al.[31] synthesized a two-dimensional hierarchical Pd/SnO2

of Sn-based
Figure 77h
structure, (Figure 7h),
h),
), and the ultra
ultra-thin Pd nanocrystals are extensively covered by SnO2
nanoparticles. This special structure can effectively realize a large amount of electron transfer, and
improve the selectivity of methanol products, the adsorption of CO2 on the tin oxide surface, and
the stability of the catalyst.
Compounding with conductive carbon materials is one of the effective ways to control the
morphology of the Sn- based catalysts. Lei et al.[61] proposed an ideal material model for an ultra-
Sn-based
Sn -based
thin metal Sn layer, which was confined in the middle of the graphene layer. Served as "spacer
layer", the ultra-

ultra-thin
ultra -thin Sn quantum sheets facilitates electrolyte diffusion into the graphene matrix,
and as an active site for effective carbon dioxide adsorption. In addition, the highly conductive
graphene layer has a rapid electron penetration effect on the metal ultrathin layer. From Figure 8a,
it proved that, coated with carbon, an ultra-thin SnO2 layer was synthesized by hydrothermal
method, and calcined at elevated temperature to obtain dispersed Sn quantum sheets. Among them,
graphene can effectively avoid the oxidation of tin metal at ambient atmosphere. In Figure 8b-c,
confined in graphene, the Sn quantum layers appeared a maximum faradaic efficiency of 89% at -

1.8 V (vs. SCE), which was higher than bulk Sn and 15 nm Sn nanoparticles that mixed with
graphene. Good stability of Sn quantum sheets can be confirmed by a continuous long-term
stability measurement. The results gave information that the faradaic efficiency of formic acid can
be largely preserved over 50 h without a significant decay. In conclusion, the presence of highly
Accepted Article
conductive graphene plays aan important role in enhancing the electronic conductivity in total and
enduring fast electron penetration to the ultrathin Sn quantum sheet layers. And under the
protection of graphene, the oxidation of the highly reactive Sn quantum sheet can be furtherly
avoided. Moreover, higher

higher electrochemical active surface area (ECSA) can expose more active sites,
thus efficiently adsorb CO2. Therefore, adding highly conductive materials and preparing catalysts
with high ECSA are effective measures for improving activity. Similarly, a Sn modified N-doped
carbon nanofiber hybrid catalyst was developed. Wallace et al.[23b] obtained the catalyst through
straight forward electrospinning technique ((Figure 8d-f). Due to the interaction between Sn and
pyridine N, the faradaic efficiency of formic acid reached 60% under the action of moderate
overpotential, while the highest faradaic efficiency of CO was 91% under the lower overpotential of
490 mV.
Liu et al.[2
[20]
[200]]
reported a new type of Sn nanoparticles modified 3D carbon nanot
nanotube aerogel
(Figure 8g).
). The 3D porous structured catalyst provides high specific surface area and mass
transfer channel, which can increase the transfer of electrons and reaction intermediate during the
reaction. The special 3D porous hierarchical structu

structure leads to an increase in current density, and
effectively increases the selectivity of formate. It has high stability at -0.96 V (vs. RHE). The 3D
Agls/CC electrode reached a higher current density of 32.9 mA cm-2 and achieves a
Sn/CNT-Agls/CC
maximum faradaic efficiency of formic acid of 82.7% at a low overpotential of 361 mV (Figure
8h-i).[80]
From these reported studies, the effect of morphology control on the performance of Sn-based
catalysts for the CO2RR is crucial. Increasing the amount of exposed active sites and accelerating

the charge transfer speed by controlling the Sn-based morphology is an effective way to enhance
the catalytic activity.
4.2 Size effects
Similar to the shape effect on the electrochemical catalytic performance, the material size is
Accepted Article
another decisive for the electrochemical CO2RR. Compared with a large-sized catalyst, a catalyst
with an ultra-
ultra-small
ultra-small
small size can ensure enough active sites, more catalyst particles, and a larger contact
area, so it can effectively increase the amount of CO2 molecular adsorption and product conversion
efficiency. Moreover, the small size of catalyst is also beneficial to reduce energy loss during the
reaction and improve energy conversion efficiency. As early as 2014, Meyer et al.[1a] prepared a
controllable size
size of SnO2 nanocrystals supported on graphene with hydrothermal method, as shown
in Figure 9a-b.
aa--b
b.. Figure 99c gives the information that, at a low potential of -0.34 V (vs. SCE), the
current density is greater than 10 mA cm-2, and the faradaic efficiency of formic acid is up to 93%.
The reasons for this high stability and catalytic performance are mainly including the two parts. On
the one hand, the graphene support is a three

three-dimensional porous surface structure, and a higher
surface area is conducive

conducive to CO2 transport and electron transfer. On the other hand, the surface of
tin oxide nanoparticles exhibits a strong interaction with CO2, which is conducive to protonation. In
the process of the optimization the size of the catalyst, it was found that the performance of 5 nm
nanoparticles was the best, as shown in Figure 9d. In addition, the catalyst can maintain a higher
yield of HCOOH for 18 hours. This work shows that the electronic structure of Sn
Sn-based catalysts
can be regulated by adjusting tthe size of the catalysts, thus enhancing the catalytic activity of
CO2RR.
Other nanostructures of small size also have similar properties, and on this basis, the small size
catalysts with the synergistic hollow structure reveal a multiple-fold improvement in catalytic
performance. In 2018, Zheng et al.[68] synthesized SnO2 loaded hollow carbon spheres with a size of
5 nm (Figure 9e-f). Compared with tin oxide nanoparticle hollow spheres or hollow carbon spheres,

which were prepared under the same conditions, the generation of hydrogen is effectively
suppressed, while the formic acid yield is significant enhanced. In 2019, Zeng et al.[58] successfully
synthesized ultra-thin SnO2 nanomaterials with high grain boundaries below 2 nm (Figure 9g-h). In
electrochemical applications, CO2 can be effectively reduced to formic acid. Yang et al.[67] used
Accepted Article
oxidation to obtain ultra-
ultra-small-sized
ultra - SnO2 nanoparticles (5 nm) (Figure 9i). Achieving a current
density of 147 mA cm--22 at -0.95 V (vs. RHE), and the faradaic efficiency of the C1 product is as
high as 97%. In 2019, Bejtka et al.[21b] developed a highly efficient and stable SnO2 catalyst for
Figure 99j
CO2RR (Figure 9j-k).
j--k
k).
). This SnO2 nano-catalyst is highly crystallized from 8-20 nm with a
mesoporous structure, and there aare a large number of grain boundaries, which can increase the
specific surface area and pore volume of the catalyst, thus the electrocatalytic activity of CO 2RR is
significantly improved. Furthermore, the electrocatalytic activity can stably maintain withi
within 5 hours.
Del Castillo et al.[[21

[21a]
21a]
a]
investigated the effect of Sn particle size and load capacity the carbon support
for catalytic performance. The small particle size (d<150 nm) Sn nanoparticles and lower loading
catalysts displayed better catalytic perfo

performance and furtherly improved catalytic activity.
From these reported studies, we can see that the small

small-sized Sn-based catalysts, especially
those rich in grain boundaries, have unique advantages in connection methods, electron transfer,
surface area, which

which can promote protonation and charge transfer, thus result in high faradaic
efficiency and current density for CO2RR.
4.3
.3 Compound modifications
Sn-based
based catalysts generally demonstrates a high overpotentials for CO2RR. Recent studies
indicate that the synergistic effect of conductive supports and Sn

Sn-based catalysts can effectively
reduce the overpotential during the reaction. In addition, the conductive carrier itself has a more
porous structure, offering a larger surface area for CO2 adsorption. During the reaction, the
conductive carrier helps to uniformly disperse the Sn-based material, so the aggregation of
nanostructures is reduced, which can increase the number of active sites and promote electron

transfer and ultimately reduces the overpotential.[44] In 2019, Hu et al.[71] discovered a three-
dimensional porous carbon nano conductive carrier. SnO2 nanoparticles can be evenly dispersed on
the conductive carrier to form rich pore structure (Figure 10a-b). Compared with ordinary SnO2
supported and activated carbon nanostructures (Figure 10c), it has better catalytic performance for
Accepted Article
CO2RR. When the potential is -0.85 V (vs. RHE), the current density reaches 29 mA cm-2, and the
faradaic efficiency of HCOOH reaches 92%. Owing to the porous carbon nanostructure, the large
number of micropores can inhibit the transfer of protons to the active site, so as to stop the
hydrogen reduction process, which can improve the formic acid yield
yield, and provide a path for charge
transport to obtain a larger current density.
In addition to the porous structure, doping carbon carriers with non

non-metal elements has a great
performance. In 2018, Zhang et al.[69] synthesized a small-sized SnO2@N-rGO

impact on catalytic performance
catalyst to ef fective reduce CO2 to HCOOH (Figure 10d-f). The catalyst demonstrates the highest
effective
faradaic efficiency of 89% for the C1 products with a current density of 21.3 mA cm-2 at -0.8 V (vs.
RHE). The enhanced performance is attributed to the ensemble effect of N doping and SnO2
nanocrystals on graphene surface, which increases the CO2 adsorption. Therefore, the composite
catalyst demonstrates a high product selectivity at low potential, and can maintain high stability
within 20 hours. In 2019, Liu et al.[70] first prepared the SnO2-NFs catalyst by sulfur desulfurization,
and then thus obtained the SnO2-NCs catalyst by acid etching (Figure 10g). Both catalysts are rich
and porous, and the electrochemically active area and surface area have been obviously improved
(Figure 10h-i).
--ii). 1.0 V ((vs. RHE), the current density reached 10.3 and 9.4 mA cm-2, respectively,
). At --1.0
aradaic efficiency of formic acid was as high as 72.6% and 82.1% ((Figure 10j-k). The
while the faradaic
control experiment proves that the obvious enhancement of catalytic activity comes from the stable
three-dimensional porous special structure, high specific surface area and excellent wettability.
Furthermore, the catalyst has stable catalytic performance within 12 hours of reaction time, and the
structure is kept intact.

The discovery and application of special shell structure are also can bring new research ideas.
In 2020, Hou et al.[1b] combined in-situ carbon with SnO2 nanostructures by hydrothermal method,
after which this structure was embedded into the N-doped carbon (NC) shell to prepare SnO2-
NC@EEG nanostructures around 10 nm. The charge transfer is accelerated and the CO 2 adsorption
Accepted Article
on the catalyst surface is improved, because SnO2 nanosheets are confined in the NC shell. The
catalyst has a low starting potential. At a potential of -1.2 V (vs. RHE), the faradaic efficiency of
the C1 product reaches the maximum of about 78%. Similarly, Hu et al.[23c] synthesized tin oxide
(SnO) nanoparticles with ultra-small size (~2.6 nm) (Figure 11a). This catalyst was prepared by
with ultra
loading Sn oxide nanoparticles on carbon black. As shown in Figure 11b, in the range of -0.5 to -
0.9 V (vs. RHE), the total faradaic efficiency of the C1 product gradually increases, reaching about
95% at -0.9
0.9 V. During the process of studies on the reaction mechanism, there were various
discoveries. First, the ultra

ultra-small size of the catalyst increases the number of nanoparticles, and thus
the density of the effective catalyst component increases as well. Secondly, the conductive matrix
increases the conductivity of the catalyst, and provides channels for electron transfer. However, as
shown in Figure 11
111c,
1cc,, the catalyst shows a very sma
small nanometer size highly aggregated. The
aggregation of nanoparticles reduces the specific surface area and contact area of the catalyst to a
certain extent, which may have a negative effect on the catalytic performance.
In addition to the conductive matri

matrix, the modification of metal atoms doping can also enhance
Sn-based catalysts. In 2019, Guan et al.[5] prepared Bi-doped SnO

the catalytic performance of Sn
foam-based materials by hydrothermal synthesis (Figure 11d-e). The

nanosheets grown on Cu foam
catalyst was applied to the CO2RR, and the main reduction product is formic acid. At -1.7 V (vs.
Ag/AgCl), the highest faradaic efficiency of formic acid reaches 93%, which better than the SnO on
the Cu foam catalyst (Figure 11f). When the current density is 12 mA cm-2, it can maintain good
chemical stability within 30 hours (Figure 11g). The mechanism research proves that the doping of
Bi element can maintain the stability of a large amount of divalent tin (Sn2+) on the surface of the

catalyst, so it is not easy to be reduced to metallic tin (Sn). Bi doping improves the selectivity of the
product, and the application of the Cu foam-based materials also has a positive effect on the
catalytic performance. At present, there exist fewer researches on metal-doped or composite tin
oxide catalysts.
Accepted Article
Compounding with other metal compounds is also one of the effective ways to enhance the
activity of Sn- based catalysts. Wang et al.[81] used the electrodeposition-annealing-electroreduction

Sn-based
Sn -based
approach to prepared the Cu foam electrode that modified by the partially reduced oxides (SnOx and
CuOx) (A-Cu/SnO (Figure 112a-b). In order to improve the long-term stability and high product
Cu/SnO2) (Figure
selectivity of tin oxide catalysts, metal oxide carriers were applied to the modification of catalysts.
Park et al.[82]] designed and synthesized γγ-alumina (γ-Al2O3) support and loaded it onto the surface
of SnO2 electrocatalyst. ((Figure 12c-f). Due to the strong interaction of support and catalyst, the
particle size, morphology, and crystallinity of SnO2 were effectively maintained, which lead to a
good stability of the electrocatalyst. Xiao et al.[73] reported an original type of cube-like
Zn2SnO4/SnO2 hetero structure catalyst ((Figure 12g-j), which realized the efficient transfer of
interfacial charge
charge and reduced the kinetic barriers of the reduction process.
It is also one of the effective ways to enhance the performance of Sn

Sn-based catalysts by
catalysts. Kang et al.[83] reported

directly modifying the surface of the catalyst or the support of the catalysts
that, treated with ammonia, the nitrogenous SnO2 catalyst showed excellent electrocatalytic
reduction activity for the electron negative nature of N atoms ((Figure 12k-n). The faradaic
efficiency of formic acid reached 90% and the current density was 4 mA cm-2 at -0.65 V (vs. RHE).
Similarly, Gong et al.[[8

[84]
844]]
synthesized N-doped SnO2 nanoparticles, so a large number of oxygen
vacancies were introduced. The faradaic efficiency of C1 product reached 93%, which inhibited the
release of hydrogen in a large potential range.
4.4 Defect Engineering
Plentiful defect sites and carrier density can not only enhance the conductivity of the

electrocatalyst but also enhance the density of exposed active sites. For example, Qiu et al.[75]
focused on introducing defect engineering strategies, designing and synthesizing carbon foam-
supported SnOx nanosheets with oxygen-enriched vacancies. The catalyst exhibited high product
selectivity, demonstrating the highest faradaic efficiency of 86% with the highest current density of
Accepted Article
30 mA cm-2 for formic acid production. Oxygen vacancy defects significantly increase the active
site of the catalyst, promote electron transport efficiency, and enhance CO2 adsorption and
activation.
Similarly, the defect sites of Sn

Sn-based sulfides also promote the catalyst performance. Zhu et
al.[77] designed and synthesized a composite Ag nanowire and a defective SnS 2 nanosheet catalyst.
Metal Ag nanowires increased the carrier density of the SnS2 catalyst. At -0.8 V (vs. RHE), the
faradaic efficiency of carbon product is up to 83%. Abundant SnS2 defect sites and increased carrier
density of Ag can effectively improve the conductivity of the composite catalyst, increase the
adsorption of CO2 molecules

molecules, and ultimately promote the improvement of catalyst performance.
5.. Summary and perspectives
In general, we provide a comprehensive review of recent advances in Sn

Sn-based catalysts for
CO2RR. Although researchers have tried various strategies to improve the activity of Sn
Sn-based
catalysts, including morphology and size control, surface modification, and defects construction,
Sn-based
based catalyst demonstrates a poor reaction current density and stability in H-type cell, due to
the limitation of mass transfer. Therefore, it is crucial to further understand the mechanism of
electrochemical reduction of CO2 by Sn-based catalysts to enhance the catalytic activity. With
respect to these problems, we ppropose several strategies to develop an efficient Sn-based catalyst
for CO2RR:
1. It is expected to enhance the current density by controlling the synthesis methods to reduce the
size of the Sn-based catalysts to expose more active sites and increase the electrochemically active
surface area, such as reducing the thickness of the catalysts to the atomic size. Such as Zeng et al.[58]

designed Ni-doped ultra-thin SnS2 nanosheets through element doping engineering. This thin
atomic layer catalyst can effectively reduce CO2 to formate, achieving the largest current density of
19.6 mA cm-2 at -0.9 V (vs. RHE), and the faradaic efficiency of the carbon product is stably
maintained at 90%.
Accepted Article
2. Carbon coating on the surface of the catalyst, especially the carbon materials modified by
composite functional groups, such as amino group and hydroxyl group, can not only significantly
increase the conductivity of the catalyst and accelerate the rate of charge transfer, but also can
regulate the electronic structure of the Sn

Sn-based catalyst to enhance the adsorption capacity of CO2
and the reaction intermediates. Moreover, carbon coating can alleviate the corrosion of catalysts by
electrolyte and enhance Sn-based catalyst. For example, Liu et al.[35] reported a
enhance the stability of Sn
hollow nanorod that was formed by amino

amino-functionalized carbon-modified SnS nanosheets. After
the amino-modification,
modification, the current density and formic acid productivity of SnS catal
catalysts were
remarkably enhanced.
3. Optimizing reactors is one of the effective ways to improve current density and stability of Sn-
based catalysts. Due to the low solubility of CO2 in electrolyte, the reaction activity in traditional H-
type cell is seriously

seriously limited by the mass transfer rate. The continuous
continuous-flow electrolyzers with gas
diffusion electrodes (GDE) can increase the concentration of CO2 participating in the reaction and
provide a high surface area for the electrochemical reaction to significantly enhanced the current
density. The degradation of catalysts is not only related to itself, but also to the operating
environment. In the membrane

membrane-electrode assemblies (MEAs) type electrolyzer, the stability of
cathodic catalysts can be increased by avoidin

avoiding direct contact with electrolyte. In addition, the
distance between the anode and the cathode is greatly reduced in an MEA-type electrolyzer,
resulting in a very small ohmic loss, so that the CO2 reduction current density can reach the level of
industrial application. There is no doubt that integrating the MEA type devices with highly selective
tin based catalysts is a promising route to enhance the current density and durability at the same

time. For example, Xia et al.[85] replaced the traditional H-type cell with a flow cell configuration
equipped with a gas diffusion electrode, which significantly increased the current density of CO2RR
of bismuth oxides. Similarly, we can infer that using a flow cell can also enhance the mass transfer
efficiency of Sn-based catalysts to increase the reaction current density.

Accepted Article
4. In-depth
depth understanding the mechanism of electrochemical reduction of CO2 by Sn-based
catalysts is necessary. Advanced operando characterization techniques should be encouraged, such
as in situ XPS, XAS and Raman. For example, we all know that the oxide layers, oxygen vacancies
and other defects in SnOx are not stable under practical electrolysis conditions, and in this case, the
mechanism can be revealed more deeply by in situ characterization techniques. Additionally,
advanced theoretical calculations are increasingly used to assist the exploration of mechanism. In
terms of the structure-

structure-activity
structure -activity
activity relationship of catalysts, theoretical modeling and computational
studies are not systematic enough

enough. Systematic theoretical calculations can help to down-select
highly selective catalyst and its design, and predict the performance to save catalyst preparation
time. Such as the zheng et al.[31] applied the DRIFT to research the performance of the catalysts,
and explored the mechanism of the CO2RR.
Acknowledgements
This work was supported by the National Natural Science Foundation of China (Grant No.
21676288), Dalian National Laboratory For Clean Energy (DNL) Cooperation Fund, CAS (DNL
180406), the Fundamental

Fundamental Research Funds for the Central Universities and QIBEBT (Grant:
QIBEBT ZZBS 201805).
Received: ((will be filled in by the editorial staff))

Revised: ((will be filled in by the editorial staff))
Published online: ((will be filled in by the editorial staff))

Accepted Article
References
[1] a) S. Zhang, P. Kang, T. J. Meyer, J. Am. Chem. Soc. 2014, 136, 1734-1737; b) Y. Fu, T.
Wang, W. Zheng, C. Lei, B. Yang, J. Chen, Z. Li, L. Lei, C. Yuan, Y. Hou, ACS Appl.
Mater. Interfaces 2020, 12, 16178-16185; c) O. S. Bushuyev, P. De Luna, C. T. Dinh, L.
Tao, G. Saur, J. van de Lagemaat, S. O. Kelley, E. H. Sargent, Joule 2018, 2, 825-832; d) R.
Francke, B. Schille, M. Roemelt, Chem. Rev. (Washington, DC, U. S.) 2018, 118, 4631-
4701; e) Y. Hou, M. Qiu, M. G. Kim, P. Liu, G. Nam, T. Zhang, X. Zhuang, B. Yang, J.

Cho, M. Chen, C. Yuan, L. Lei, X. Feng, Nat. Commun. 2019, 10, 1392; f) T. Wang, Q.
Zhao, Y. Fu, C. Lei, B. Yang, Z. Li, L. Lei, G. Wu, Y. Hou, Small Methods 2019, 3.
1900210.
[2] a) N. Mac Dowell, P. S. Fennell, N. Shah, G. C. Maitland, Nat. Clim. Change 2017, 7, 243-
Accepted Article
249; b) S. Chu, A. Majumdar, Nature 2012, 488, 294-303.
[3] a) W. Zhang, Y. Hu, L. Ma, G. Zhu, Y. Wang, X. Xue, R. Chen, S. Yang, Z. Jin, Adv. Sci.
2018,, 55,, 1700275; b) J. Pan, Y. Sun, P. Deng, F. Yang, S. Chen, Q. Zhou, H. S. Park, H. Liu,
B. Yu Xia, Appl Catal., B 2019, 255; c) F. Yang, A. Chen, P. L. Deng, Y. Zhou, Z. Shahid,
Appl.. Catal.
H. Liu, B. Y. Xia, Chem. Sci. Int. J. 2019, 10, 7975-7981.
[4] a) Z. Miao, P. Hu, C. Nie, H. Xie, W. Fu, Q. Li, J. Energy Chem. 2019, 38, 114-118; b) H.
Yang, Y. Huang, J. Deng, Y. Wu, N. Han, C. Zha, L. Li, Y. Li, J. Energy Chem. 2019, 37,
93-96.
96.
[5] X. An, S. Li, A. Yoshida, T. Yu, Z. Wang, X. Hao, A. Abudula, G. Gu

Guan, ACS Appl. Mater.
Interfaces 2019
2019,, 11
11, 42114-42122.
[6] a) J. Wang, X. Li, J. Zheng, J. Cao, X. Hao, Z. Wang, A. Abudula, G. Guan, Energy
Manage.. 2018, 164, 122-131; b) H. J. Lee, D. C. Kang, S. H. Pyen, M. Shin, Y. W.

Convers.. Manage
Convers
Suh, H. Han, C.
C.-H.H. Shin, Appl. Catal., A 2017, 531, 13-20.
--H.
[7] S. Verma, B. Kim, H. R. Jhong, S. Ma, P. J. Kenis, ChemSusChem 2016, 9, 1972-1979.
[8] a) W. Zhu, R. Michalsky, Ö. Metin, H. Lv, S. Guo, C. J. Wright, X. Sun, A. A. Peterson, S.
Sun, J. Am. Chem. Soc. 2013, 135, 16833-16836; b) S. Zhu, X. Qin, Q. Wang, T. Li, R. Tao,
M. Gu, M. Shao, JJ. Mater. Chem. A 2019, 7, 16954-16961; c) D. Kim, C. Xie, N. Becknell,
Y. Yu, M. Karamad, K. Chan, E. J. Crumlin, J. K. Norskov, P. Yang, J. Am. Chem. Soc.
2017, 139, 8329-8336.
[9] a) Q. Lu, J. Rosen, Y. Zhou, G. S. Hutchings, Y. C. Kimmel, J. G. Chen, F. Jiao, Nat.
Commun. 2014, 5, 3242; b) C. Kim, H. S. Jeon, T. Eom, M. S. Jee, H. Kim, C. M. Friend, B.

K. Min, Y. J. Hwang, J. Am. Chem. Soc. 2015, 137, 13844-13850; c) J. Gao, C. Zhu, M.
Zhu, Y. Fu, H. Huang, Y. Liu, Z. Kang, ACS Sustainable Chem. Eng. 2019, 7, 3536-3543.
[10] a) H. Z. Dunfeng Gao, Jing Wang, Shu Miao, Fan Yang, Guoxiong Wang, Jianguo Wang,
and Xinhe Bao, J. Am. Chem. Soc. 2015; b) R. Chen, M. Cao, W. Yang, H. Wang, S. Zhang,
Accepted Article
Chem.Commun. 2019, 55, 9805-9808.
H. Li, R. Cao, Chem
[11] a) M. Mikkelsen, M. Jørgensen, F. C. Krebs, Energy Environ. Sci. 2010, 3, 43-81; b) Y.
Chen, C. W. Li, M. W. Kanan, J. Am. Chem. Soc. 2012, 134, 19969-19972.
[12] S. Zhao, S. Li, T. Guo, S. Zhang, J. Wang, Y. Wu, Y. Chen, Nano-Micro Lett. 2019, 11, 62.
[13] Z. Chen, S. Yao, L. Liu, J. Mater. Chem. A 2017, 5, 24651-24656.
[14] a) A. Del Castillo, M. Alvarez

Alvarez-Guerra, J. Solla-Gullón, A. Sáez, V. Montiel, A. Irabien,
Appl. Energy 2015

2015, 157, 165-173; b) K. Bejtka, J. Zeng, A. Sacco, M. Castellino, S.
Hernández, M. A. Farkhondehfal, U. Savino, S. Ansaloni, C. F. Pirri, A. Chiodoni, ACS
Mater. 2019, 2, 3081-3091.

Appl. Energy Mater
[15] a) C. Reller, R. Krause, E. Volkova, B. Schmid, S. Neubauer, A. Rucki, M. Schuster, G.
Schmid, Adv. Energy Mater. 2017, 7, 1602114; b) X. Z. Zhen Liu, Selcuk Poyraz, Sumedh
P. Surwade, and Sanjeev K. Manohar, J. Am. Chem. Soc. 2010, 132, 13158–13159.
[16] W. Xu, Small 2016, 12, 5710-5719; b) Y. Zhao, J. Liang, C. Wang,

a) Z. K. Yang, L. Lin, A. W
J. Ma, G. G. Wallace, Adv. Energy Mater. 2018, 8, 1702524; c) J. Gu, F. Heroguel, J.
Luterbacher, X. Hu, Angew. Chem., Int. Ed. 2018, 57, 2943-2947.
[17] H. Fan, H. Yu, Y. Zhang, Y. Zheng, Y. Luo, Z. Dai, B. Li, Y. Zong, Q. Yan, Angew. Chem.,
Int. Ed. 2017

2017,, 56
56,, 12566
12566-12570.
[18] C. B. Hiragond, H. Kim, J. Lee, S. Sorcar, C. Erkey, S.-I. In, Catalysts 2020, 10, 98.
[19] Y. Yang, J. W. Lee, Chem. Sci. 2019, 10, 3905-3926.
[20] J. Wu, Y. Huang, W. Ye, Y. Li, Adv. Sci. (Weinheim, Ger.) 2017, 4, 1700194.
[21] S. Xie, Q. Zhang, G. Liu, Y. Wang, Chem. Commun. (Cambridge, U. K.) 2016, 52, 35-59.

[22] M. T. Nasir Shehzad, Khairiraihanna Johari, Thanabalan Murugesan, Murid Hussain, J. CO2
Util. 2018, 26, 98-122.
[23] a) A. M. a. R. T. Yoshio Hori, J. Chem. SOC., Faradaic Trans. 1989, 85, 2309-2326; b) R. J.
Lim, M. Xie, M. A. Sk, J. M. Lee, A. Fisher, X. Wang, K. H. Lim, Catal. Today 2014, 233,
Accepted Article
169-180.
180.
[24] R. Xu, Anal. Methods 2013, 5,1086-1097.

J. Hong, W. Zhang, J. Ren, R
[25] T. B. Jan Ronge´, David Martel, Carlo Nervi, Luca Boarino, Francis Taulelle, Gero Decher,
Silvia Bordigac and Johan A. Martens, Chem. Soc. Rev. 2014, 43, 7963-7981.
[26] B. Kumar, M. Llorente, J. Froehlich, T. Dang, A. Sathrum, C. P. Kubiak, Annu. Rev. Phys.
Chem. 2012
2012,, 63
63,, 541
541-569.
[27] Jean-Michel Savéant1, pans 2014, 42, 14990-

G. P. Cyrille Costentin1, Marc Robert1, and Jean
14994.
[28] H. Wang, Y. W. Zhou, W. B. Cai, Curr. Opin. Electrochem. 2017, 1, 73-79.
[29] M. Grossutti, J. J. Leitch, R. Seenath, M. Karaskiewicz, J. Lipkowski, Langmuir 2015, 31,
4411-4418.
--4418.
4418.
[30] M. F. Baruch, J. E. Pander, J. L. White, A. B. Bocarsly, ACS Catal. 2015, 5, 3148-3156.
[31] W. Zhang, Q. Qin, L. Dai, R. Qin, X. Zhao, X. Chen, D. Ou, J. Chen, T. T. Chuong, B. Wu,
N. Zheng, Angew. Chem., Int. Ed. 2018, 57, 9475-9479.
[32] a) M. B. Ross, P. De Luna, Y. Li, C. T. Dinh, D. Kim, P. Yang, E. H. Sargent, Nat. Catal.
2019,, 22,, 648-

648-658;
648 -658;
658; b) Y. Y. Birdja, E. Pérez-Gallent, M. C. Figueiredo, A. J. Göttle, F. Calle-
Vallejo, M. T. M. Koper, Nat. Energy 2019, 4, 732-745; c) M. Manikandan, T. Tanabe, P.
Li, S. Ueda, G. V. Ramesh, R. Kodiyath, J. Wang, T. Hara, A. Dakshanamoorthy, S.
Ishihara, K. Ariga, J. Ye, N. Umezawa, H. Abe, ACS Appl. Mater. Interfaces 2014, 6, 3790-
3793.

[33] Z. Chen, M. R. Gao, N. Duan, J. Zhang, Y. Q. Zhang, T. Fan, J. Zhang, Y. Dong, J. Li, Q.
Liu, X. Yi, J. L. Luo, Appl. Catal., B 2020, 277, 119252.
[34] X. An, S. Li, A. Yoshida, Z. Wang, X. Hao, A. Abudula, G. Guan, ACS Sustainable Chem.
Eng. 2019, 7, 9360-9368.

Accepted Article
[35] Z. Chen, X. Zhang, M. Jiao, K. Mou, X. Zhang, L. Liu, Adv. Energy Mater. 2020, 10,
1903664.
[36] a) H. Wonda, H. Shin, J. Koh, J. Chung, H. S. Lee, H. Kim, S. I. Woo, Angew. Chem., Int.
Ed. 2016
2016,, 55 9297-9300; b) D. Raciti, K. J. Livi, C. Wang, Nano Lett. 2015, 15, 6829-6835.
55,, 9297
[37] N. Arora, B. R. Jagirdar, Phys. Chem. Chem. Phys. 2014, 16, 11381-11389.
[38] A. M. Ismail, G. F. Samu, Á. Balog, E. Csapó, C. Janáky, ACS Energy Lett. 2018, 4, 48-53.
[39] X. Bai, W. Chen, C. Zhao, S. Li, Y. Song, R. Ge, W. Wei, Y. Sun, Angew. Chem., Int. Ed.
2017,, 56
56,, 12219-
12219-12223.
12219 -12223.
12223.
[40] J. Zeng, K. Bejtka, W. Ju, M. Castellino, A. Chiodoni, A. Sacco, M. A. Farkhondehfal, S.
Hernández, D. Rentsch, C. Battaglia, C. F. Pirri, Appl. Catal., B 2018, 236, 475-482.
[41] Y. Zhang, X. Zhang, A. M. Bond, J. Zhang, Phys. Chem. Chem. Phys. 2018, 20, 5936-5941.
[42] C. Zhao, J. Wang, Chem. Eng. J. 2016, 293, 161-170.
[43] J.-M. Fontmorin, E. H. Yu, J. CO2 Util. 2019, 32, 1-10.

S. Rasul, A. Pugnant, H. Xiang, J.
[44] Q. Zhang, Y. Zhang, J. Mao, J. Liu, Y. Zhou, D. Guay, J. Qiao, ChemSusChem 2019, 12,
1443-1450.
--1450.
1450.
[45] Y. Zhao, B. Zhao, J. Liu, G. Chen, R. Gao, S. Yao, M. Li, Q. Zhang, L. Gu, J. Xie, X. Wen,
L. Z. Wu, C. H. Tung, D. Ma, T. Zhang, Angew. Chem., Int. Ed. 2016, 55, 4215-4219.
[46] S. Huo, Z. Weng, Z. Wu, Y. Zhong, Y. Wu, J. Fang, H. Wang, ACS Appl. Mater. Interfaces
2017, 9, 28519-28526.
[47] Y. Chen, M. W. Kanan, J. Am. Chem. Soc. 2012, 134, 1986-1989.
[48] J. Wu, F. G. Risalvato, S. Ma, X. D. Zhou, J. Mater. Chem. A 2014, 2, 1647-1651.

[49] Y. Li, J. Qiao, X. Zhang, T. Lei, A. Girma, Y. Liu, J. Zhang, ChemElectroChem 2016, 3,
1618-1628.
[50] T. Kida, T. Doi, K. Shimanoe, Chem. Mater. 2010, 22, 2662-2667.
[51] H. Ge, Z. Gu, P. Han, H. Shen, A. M. Al-Enizi, L. Zhang, G. Zheng, J. Colloid Interface Sci.
Accepted Article
2018,, 531
531,, 564-
564-569.
564 -569.
569.
[52] F. Li, L. Chen, G. P. Knowles, D. R. MacFarlane, J. Zhang, Angew. Chem., Int. Ed. 2017, 56,
505-509.
--509.
509.
[53] a) H. Kim, H. Kim, S. Muhammad, J. H. Um, M. S. A. Sher Shah, P. J. Yoo, W.

W.-S. Yoon, J.
Power Sources 2020

2020, 446, 227321; b) Q. Wang, D. Wang, M. Wu, B. Liu, J. Chen, T. Wang,
J. Chen, J. Phys. Chem. Solids 2011, 72, 630-636; c) N. Han, Y. Wang, J. Deng, J. Zhou, Y.
Wu, H. Yang, P. Ding, Y. Li, J. Mater. Chem. A 2019, 7, 1267-1272.
[54] a) L. Fan, Z. Xia, M. Xu, Y. Lu, Z. Li, Adv. Funct. Mater. 2018, 28; b) B. Zhang, L. Sun, Y.
Wang, S. Chen, J. Zhang, J. Energy Chem. 2020, 41, 7-14; c) B. Kumar, V. Atla, J. P. Brian,
S. Kumari, T. Q. Nguyen, M. Sunkara, J. M. Spurgeon, Angew. Chem., Int. Ed. 2017, 56,
3645-3649.
--3649.
3649.
[55] a) J. Ba, J. Polleux, M. Antonietti, M. Niederberger, Adv. Mater. 2005, 17, 2509-2512; b) Q.
Zhao, Y. Gao, X. Bai, C. Wu, Y. Xie, Eur. J. Inorg. Chem. 2006, 45, 1643-1648; c) C. Yu, J.
C. Yu, F. Wang, H. Wen, Y. Tang, CrystEngComm 2010, 12, 341-343; d) C. L. Qin Kuang,
Zhong Lin Wang, Zhaoxiong Xie, and Lansun Zheng, J. Am. Chem. Soc. 2007, 129, 6070;
e) S. Sun, G. Meng, G. Zhang, J. P. Masse, L. Zhang, Chem. Eur. J. 2007, 13, 9087-9092.
[56] a) C. W. Li, J. Ciston, M. W. Kanan, Nature 2014, 508, 504-507; b) X. Feng, K. Jiang, S.
Fan, M. W. Kanan, J. Am. Chem. Soc. 2015, 137, 4606-4609.
[57] K. S. Kim, W. J. Kim, H. K. Lim, E. K. Lee, H. Kim, ACS Catal. 2016, 6, 4443-4448.
[58] A. Zhang, R. He, H. Li, Y. Chen, T. Kong, K. Li, H. Ju, J. Zhu, W. Zhu, J. Zeng, Angew.
Chem., Int. Ed. 2018, 57, 10954-10958.

[59] X. Zheng, P. De Luna, F. P. García de Arquer, B. Zhang, N. Becknell, M. B. Ross, Y. Li, M.
N. Banis, Y. Li, M. Liu, O. Voznyy, C. T. Dinh, T. Zhuang, P. Stadler, Y. Cui, X. Du, P.
Yang, E. H. Sargent, Joule 2017, 1, 794-805.
[60] F. Li, L. Chen, M. Xue, T. Williams, Y. Zhang, D. R. MacFarlane, J. Zhang, Nano Energy
Accepted Article
2017,, 31
31,, 270-
270-277.
270 -277.
277.
[61] F. Lei, W. Liu, Y. Sun, J. Xu, K. Liu, L. Liang, T. Yao, B. Pan, S. Wei, Y. Xie, Nat.
Commun.. 2016
Commun 2016,, 77,, 12697.
[62] X. Zhang, F. Li, Y. Zhang, Alan M. Bond, J. Zhang, J. Mater. Chem. A 2018, 6, 7851-7858.
[63] C. Chen, Y. Pang, F. Zhang, J. Zhong, B. Zhang, Z. Cheng, J. Mater. Chem. A 2018, 6,
19621-19630.
19621-
19621-19630.
19630.
[64] G. Wen, D. U. Lee, B. Ren, F. M. Hassan, G. Jia

Jiang, Z. P. Cano, J. Gostick, E. Croiset, Z.
Bai, L. Yang, Z. Chen, Adv. Energy Mater. 2018, 8, 1802427.
[65] S. Liu, F. Pang, Q. Zhang, R. Guo, Z. Wang, Y. Wang, W. Zhang, J. Ou, Appl. Mater.
Today 2018
2018,, 13
13,, 135
135-143.
[66] Y. H. Ng, R. Amal, ACS Sustainable Chem. Eng. 2018, 6,

R. Daiyan, X. Lu, W. H. Saputera, Y
1670-1679.
--1679.
1679.
[67] C. Liang, B. Kim, S. Yang, Y. L. Yang Liu, C. Francisco Woellner, Z. Li, R. Vajtai, W.
Yang, J. Wu, P. J. A. Kenis, Pulickel M. Ajayan, J. Mater. Chem. A 2018, 6, 10313-10319.
[68] Y. Yiliguma, Z. Wang, C. Yang, A. Guan, L. Shang, A. M. Al

Al-Enizi, L. Zhang, G. Zheng, J.
Mater. Chem. A 2018

2018, 6, 20121-20127.
[69] B. Zhang, Z. Guo, Z. Zuo, W. Pan, J. Zhang, Appl. Catal., B 2018, 239, 441-449.
[70] X. Zhang, Z. Chen, K. Mou, M. Jiao, X. Zhang, L. Liu, Nanoscale 2019, 11, 18715-18722.
[71] Y. He, W. J. Jiang, Y. Zhang, L. B. Huang, J. S. Hu, J. Mater. Chem. A 2019, 7, 18428-
18433.

[72] R. Daiyan, E. C. Lovell, N. M. Bedford, W. H. Saputera, K. H. Wu, S. Lim, J. Horlyck, Y.
H. Ng, X. Lu, R. Amal, Adv. Sci. (Weinheim, Ger.) 2019, 6, 1900678.
[73] K. Wang, D. Liu, P. Deng, L. Liu, S. Lu, Z. Sun, Y. Ma, Y. Wang, M. Li, B. Y. Xia, C.
Xiao, S. Ding, Nano Energy 2019, 64, 103954.

Accepted Article
[74] H. Wonda, C. H. Choi, J. Chung, M. W. Chung, E. H. Kim, S. I. Woo, ChemSusChem 2015,
8,, 3092-
3092-3098.
3092-3098.
3098.
[75] H. Li, N. Xiao, Y. Wang, C. Liu, S. Zhang, H. Zhang, J. Bai, J. Xiao, C. Li, Z. Guo, S. Zhao,
J. Qiu, J. Mater. Chem. A 2020, 8, 1779-1786.
[76] S. Back, J. Lim, N. Y. Kim, Y. H. Kim, Y. Jung, Chem. Sci. 2017, 8, 1090.
[77] R. He, X. Yuan, P. Shao, T. Duan, W. Zhu, Small 2019, 15, e1904882.
[78] J. Ye, H. Zhang, R. Yang, X. Li, L. Qi, Small 2010, 6, 296-306.
[79] H. Hu, L. Gui, W. Zhou, J. Sun, J. Xu, Q. Wang, B. He, L. Zhao, Electrochim. Acta 2018,
285,, 70-
70-77.
70 -77.
77.
[80] a) D. D. Zhu, J. L. Liu, S. Z. Qiao, Adv. Mater. 2016, 28, 3423-3452; b) b. Seunghwa Lee
Lee, ChemSusChem 2016, 9, 333-344; c) R. Kortlever, J. Shen, K. J.

and Jaeyoung Lee
Calle-Vallejo, M. T. Koper, J. Phys. Chem. Lett. 2015, 6, 4073-4082.

Schouten, F. Calle
[81] Q. Li, M. Li, S. Zhang, X. Liu, X. Zhu, Q. Ge, H. Wang, Catalysts 2019, 9, 476.
[82] Y. E. Kim, W. Lee, M. H. Youn, S. K. Jeong, H. J. Kim, J. C. Park, K. T. Park, J. Ind. Eng.
Chem. 2019
2019,, 78
78,, 73
73-78.
[83] Q. Li, Z. Wang, M. Zhang, P. Hou, P. Kang, J. Energy Chem. 2017, 26, 825-829.
[84] C. Hu, L. Zhang, L. Li, W. Zhu, W. Deng, H. Dong, Z. J. Zhao, J. Gong, Sci. China: Chem.
2019, 62, 1030-1036.
[85] P. Deng, F. Yang, Z. Wang, S. Chen, Y. Zhou, S. Zaman, B. Y. Xia, Angew. Chem., Int. Ed.
Engl. 2020, 59, 10807-10813.

Accepted Article
Figure 1. Possible reaction pathways for electrocatalytic CO 2RR in aqueous solutions.
Figure 2. a) The optimized geometry of SnO2. b-c) Summary of configurations and energies of clean SnO2 (110)
surface, including O-
O-terminated
O -terminated
terminated model from aa-axis view, b-axis view, Sn-terminated model from, a-axis view b-axis
view.. Color code: orange for oxygen, blue for tin. [33] Copyright 2020, Elsevier. d) Calculated free-energy diagram of
electrocatalytic reduction of CO2 to formate. e-f) The differential charge diagram of SnS/Aminated-C for top view and
front view, cyan and yellow indicate depletion and accumulation of electrons respectively. g) Calculated adsorption
energies of reaction intermediates.[35] Copyright 2020, WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Accepted Article
Figure 3. a) Schematic diagram of CO2 reduction process on Au-Sn nanoparticle surface. b) TEM image of the Au-Sn
catalyst. Reproduced with permission.[38] Copyright 2019, American Chemical Society. c) TEM image and size
distribution of the Pd-

Pd-Sn/C
Pd -Sn/C
Sn/C nanoparticles. Insets: high
high- resolution TEM image of the catalyst. d) The faradaic efficiency
and overpotential of Pd/C, Sn/C and alloy Pd xSn/C at the CO2 reduction potentials (0.5 M KHCO3). Reproduced with
permission.[39] Copyright 2017, Wiley

Wiley-VCH Verlag GmbH & Co. KGaA. e-f) SEM images of the Cu-Sn foam.
Reproduced with permission.[40] Copyright 2018, Elsevier. g) SEM image of electrodeposited dendritic Sn catalysts on
metal Cu substrates. h) The faradaic efficiency of the Sn/Pt, Sn/Cu, Sn/Sn and Sn/In catalysts saturated 0.5 M NaHCO 3
aqueous solutions. Reproduced with permission.[41] Copyright 2018, The Royal Society of Chemistry.
Figure 4. a) TEM image of SnO2 nanoparticles on graphene.[1a] b) Particle size dependence of faradaic efficiencies for
CO2 reduction to formate on Sn catalysts c) Fabrication of SnOx@MWCNTs catalysts. d) TEM image of the catalyst.
Reproduced with permission.[44] Copyright 2019, Wiley-VCH Verlag GmbH & Co. KGaA. e) The relation between the

catalysts structure and the products. f) Schematic illustration of SnOx nanosheets Growth on CNTs. Reproduced with
permission.[46] Copyright 2017, American Chemical Society.g) Catalyst model of the Sn/SnOx. h) The faradaic
efficiency of the catalysts. Reproduced with permission. [47] Copyright 2012, American Chemical Society. i) HRTEM
images of the as-received and annealed Sn nanoparticles. j) Effect of thickness on faradaic efficiency of products.
Reproduced with permission.[48] Copyright 2014, The Royal Society of Chemistry.

Accepted Article
Figure 5. a) The structural model of the 1D SnO 2 with wire-in-tube catalyst. b-c) SEM image and the faradaic
efficiency of the catalyst. Reproduced with permission.[54a] Copyright 2018, Wiley-VCH Verlag GmbH & Co. KGaA.
e) The TEM image and the faradaic efficiency of the SnO 2@N-CNW. Reproduced with permission.[54b] Copyright
d-e)
2017, Wiley-VCH
VCH Verlag GmbH & Co. KGaA. f) SEM image of the hollow SnO2 nanosheet catalysts. g) TEM image
of the porous SnO2 nanosheet. Reproduced with permission.[53b] Copyright 2011, The Royal Society of Chemistry.
Figure 6. a) The faradaic efficiency of the mesoporous SnO2 nanosheet catalysts. b-c) Preparation and the SEM
image of the mesoporous SnO 2 nanosheet catalyst. Reproduced with permission.[53c] Copyright 2019, The Royal Society
of Chemistry. d) The preparation of the 3D layered nanocatalysts obtained by loading mesoporous SnO2 nanosheets on
carbon cloth. e-f) The SEM image and the faradaic efficiency of the catalyst. Reproduced with permission. [52] Copyright
2017, Wiley-VCH Verlag GmbH & Co. KGaA.
Accepted Article
Figure 7. a) The model of the hollow SnO2 fiber catalyst. b-c) The SEM image and faradaic efficiency of the catalyst.
Reproduced with permission.[51] Copyright 2018, Wiley-VCH Verlag GmbH & Co. KGaA. d-e) The microscopic model
and preparation process of the mesoporous SnO2 nanoparticles. f-g) The SEM image and faradaic efficiency of the
catalyst. Reproduced with permission.[66] Copyright 2018, American Chemical Society. h) The preparation process of
the 2D hierarchical Pd/SnO2 catalyst. Reproduced with permission.[31] Copyright 2018, Wiley-VCH Verlag GmbH &
Co. KGaA.
Figure 8. a) Scheme illustration for the formation of Sn quantum sheets confined in graphene. b-c) TEM image
and faradaic efficiency of the Sn quantum sheets confined in graphene catalyst. Reproduced with permission.[61]
Copyright 2016, Springer Nature. d) Schematic illustration of the fabrication process of Sn modified N-doped carbon
nanofiber electrocatalysts. e-f) SEM image and the faradaic efficiency of products on Sn-CF1000 at -0.8 V (vs. RHE) in
CO2-saturated KHCO3 solution. Reproduced with permission.[23b] Copyright 2018, Wiley-VCH Verlag GmbH & Co.
KGaA. g) The fabrication process for the 3D Sn/CNT-Agls catalyst. h-i) SEM image and faradaic efficiency of the
Sn/CNT-Agls catalyst. Reproduced with permission.[20] Copyright 2017, The Royal Society of Chemistry.
Accepted Article
Figure 9. a) TEM image of the SnO2 nanoparticles on graphene. b) High-resolution TEM image of the catalyst. c-d)
Faradaic efficiency and particle size dependence of the catalysts. Reproduced with permission. [1a] Copyright 2014,
American Chemical Society. e) TEM image of the SnO2/C hollow spheres catalyst. f) Faradaic efficiency of the
catalysts. Reproduced with permission.[68] Copyright 2018, The Royal Society of Chemistry. g-h) TEM image and SEM
image of SnO2 na noparticles catalyst. Reproduced with permission.[58] Copyright 2018, Wiley-VCH Verlag GmbH &
nanoparticles
Co. KGaA. i) Scheme illustration for the formation of SnO 2 nanoparticles. j-k) TEM image and faradaic efficiency of
permission.[21b] Copyright 2019, The Royal Society of Chemistry.

the SnO2 nanoparticles. Reproduced with permis

Figure 10. a-b) SEM images of SnO2 porous carbon (PC) and active carbon (AC). c) The faradaic efficiency of
SnO2/PC and SnO2/AC for the CO2RR. Reproduced with permission.[71] Copyright 2019, The Royal Society of
Chemistry. d) Schematic illustration of the SnO2@N-rGO and SnO2@rGO nanocomposites. e) TEM image of the
catalyst. f) The faradaic efficiency of the catalyst for products. Reproduced with permission. [69] Copyright 2018,
Elsevier. g) Schematic illustration of the SnO2-NCs and SnO2-NFs catalysts. h-i) SEM images of SnO2-NCs and SnO2-
Accepted Article
k) The faradaic efficiency of the catalysts. Reproduced with permission. [70] Copyright 2019, The Royal Society
NFs. j-k)
of Chemistry.
Figure 11.. a) Schematic illustration of the SnO/C. b

b-c) The faradaic efficiency for products and the STEM image
of SnO/C. Reproduced with permission.[23c] Copyright 2018, Wiley-VCH Verlag GmbH & Co. KGaA. d-e) The SEM
image and TEM image of the Bi

Bi-SnO on the Cu foam catalyst. f) The TEM image of the SnO on the Cu foam. g) The
faradaic efficiency for the products of the catalysts. Reproduced with permission. [5] Copyright 2019, American
Chemical Society.

Figure 12. a) Typical SEM image of the A-Cu/SnO2 catalyst. b) The faradaic efficiency of the catalyst. Reproduced
with permission.[81] Copyright 2019, MDPI (Basel, Switzerland). c-f) The microscopic model, TEM image and
electrochemical performance of the γ-Al2O3 catalyst. Reproduced with permission.[82] Copyright 2019, Elsevier. g) The
procedure for the synthesis of Zn2SnO4/SnO2 microcube catalyst. h-j) SEM image, Faradaic efficiency and current
Accepted Article
density of the Zn2SnO4/SnO2 microcube catalyst. Reproduced with permission.[73] Copyright 2019, Elsevier. k) The
preparation process of the nitrogenous SnO2 catalyst. l-n) TEM image, faradaic efficiency and current density of the
catalyst. Reproduced with permission.[83] Copyright 2017, Elsevier.
Table 1. The standard reduction potentials for the different products of CO 2RR in pH 7.0 aqueous solution.[20]
Half−Electrochemical Thermodynamic Main Product Redox potential

Reactions (vs. SHE）
CO2+ e−→ CO2•− CO2•− -1.9 V
+ −
CO2+ 2H + 2e → HCOOH HCOOH -0.61 V
CO2+ 2H++ 2e−→ CO + H2O CO -0.53 V
+ −
CO2+ 4H + 4e → HCHO + H2O HCHO -0.48 V
+ −
CO2+ 6H + 6e → CH3OH + H2O CH3OH -0.38 V
+ −
CO2+ 8H + 8e → CH4+ 2H2O CH4 -0.24 V
+ −
2CO2+ 12H + 12e → C2H4+ 4H2O C2H4 -0.41 V
+ -
2H + 2e → H2 H2 -0.41 V
Table 2. Comparison of electrocatalytic activity for electrochemical CO2RR to formic acid on Sn-based electrodes.
Electrocatalysts Electrolyte Formate Applied potential Current density Ref.

FEmax (%) (V vs. RHE) (mA cm-2) at FEmax
[61]
Graphene confined Sn quantum sheets 0.1 M NaHCO3 89 -1.8 V vs. SCE 21.1
[13]
Sn/CNT-Agls 0.5 M KHCO3 82.7 -0.96 26.7
[41]
Cu supported dendritic Sn 0.5 M NaHCO3 67.3 -0.95 14
[62]
Ag–Sn/rGO
Sn/rGO catalyst 0.5 M NaHCO3 88.3 -0.94 21.3
[62]
Cu–Sn/rGO
Sn/rGO catalyst 0.5 M NaHCO3 87.4 -0.99 23.6
[63]
Sn layer@Cu nanoconic surface 0.1 M KHCO3 90.4 -1.1 57.7
[64]
Bi -NP/Sn
NP/Sn nanosheets 0.5 M KHCO3 94 -1.1 50
[16b]
Sn/N-doped
doped carbon nanofiber 0.5 M KHCO3 62 -0.69 11
[40]
Sn/Cu foam 0.1 M KHCO3 94 -0.8 4.7
[38]
Au-Sn
Sn nanoparticles 0.1 M NaHCO3 42 -1.1 11
[65]
Nanoporous Sn/SnO2 0.5 M KHCO3 80 -1.1 16
[39]
PdSn/C alloy electrocatalysts 0.5 M KHCO3 99 -0.43 -
[61]
Sn quantum sheets-graphene 0.1 M NaHCO3 85 -1.8 V vs. SCE 21.1
[42]
Sn deposited electrode 0.1 M KHCO3 91 -1.4 V vs. SCE 15
[54c]
SnO2 porous nanowire 0.1 M KHCO3 80 -0.8 7
[1a]
SnO2 nanocrystals on graphene 0.1 M NaHCO3 93 -0.34 V vs. SCE 10
[53c]
mesoporous SnO2 nanosheet 0.5 M NaHCO3 83 -0.5 16
[66]
mesoporous SnO2 nanoparticles 0.1 M KHCO3 75 -1.15 10.8
[54a]
SnO2 with WIT Architectures 0.1 M KHCO3 93 -0.99 -
[51]
Hollow SnO2 fiber 0.1 M KHCO3 75 -1.15 10.8
[67]
SnO2 nanoparticles (5 nm) 0.1 M KHCO3 97 -0.95 147
[14b]
SnO2 (8 nm) 0.1 M KHCO3 82 -1.06 15.3
[52]
SnO2 nanosheets on carbon cloth 0.5 M NaHCO3 80 -0.8 45

[1a]
SnO2 nanocrystals on graphene 0.1 M NaHCO3 93 -0.34 V vs. SCE 10
[68]
SnO2-hollow carbon spheres 0.1 M KHCO3 54.2 -0.9 -
[58]
SnO2 QWs 0.1 M KHCO3 90 -1.156 13.7
[54b]
SnO2@N-CNW 0.5 M NaHCO3 90 -0.8 13
[69]
SnO2@N–rGO 0.5 M NaHCO3 89 -0.8 21.3
[71]
SnO2-NCs 0.5 M KHCO3 82.4 -1.0 10.7
[71]
SnO2-NFs 0.5 M KHCO3 91.5 -1.0 11.5
[1b]
SnO2-NC@EEG 0.1 M KHCO3 93.2 -1.0 8.7
[72]
SnO2/AC 0.5 M KHCO3 92 -0.85 29
[73]
SnO2-FSP 0.1 M KHCO3 85 -1.1 23.7
[73]
Cube Zn2SnO4/SnO2 catalyst 0.1 M KHCO3 77 -1.08 5.77
Accepted Article
SnOx-MWCNT-NH NH2
OD Sn/Sn−Pb−Sb catalysts
0.5 M KHCO3
0.1 M KHCO3
77
91
-1.25 V vs. SHE
-1.4
9.6
8
[44]
[43]
[46]
Cu/SnOx-CNT 0.1 M KHCO3 89 -0.99 11.3
[74]
heat-treated
treated Sn dendrite electrode 0.1 M KHCO3 71.6 -1.36 17.1
[49]
SnOx/GDL electrode 0.5 M KHCO3 87.1 -1.6 10
[16c]
C-SnO
SnO nanoparticles (2.6 nm) 0.5 M KHCO3 95 -0.9 5
[5]
Bi-SnO
SnO nanosheets on Cu foam 0.1 M KHCO3 93 -1.5 12
[47]
Sn/SnOx 0.5 M NaHCO3 99 -0.7 -
[75]
SnOx-Cu foam 0.1 M KHCO3 86 -1.1 30
[58]
5% Ni-SnS2 nanosheets 0.1 M KHCO3 90% -0.9 19.6
[59]
Sn (S)/Au catalyst 0.1 M KHCO3 93 -0.75 55
[76]
SnS2/rGO 0.5 M NaHCO3 84.5 -0.48 13.9
[35]
NC-SnS nanosheets 0.5 M KHCO3 92.6 -0.9 52.1
[77]
Ag-SnS2 0.5 M KHCO3 83.8 -1.0 38.8
Author Biographies
Yunhui Li obtained her Ph.D. degree from Jilin University in 2006. She is
currently a professor in School of Chemistry and Environmental

current
Engineering, Changchun University of Science and Technology. Her
current research is focused on the design and synthesis of new
functionalized nano
nano-materials.
Zhipeng Chen received his Ph.D. degree in chemical engineering from the
University of Chinese Academy of Sciences in 2019. He is currently a
postdoctoral researcher and special research assistant in Qingdao Institute
of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences.
His current research interests focus on CO2 electrochemical reduction.

Prof. Licheng Liu obtained his B.Sc. degree in Chemical Engineering and
Technology from China University of Petroleum in 2002 and Ph.D.
degree in Chemical Technology from Institute of Process Engineering,
Accepted Article Chinese Academy of Sciences in 2007. He has been working at Beijing
University of Technology (2007-1020), University of Electro-
communications of Japan (2010-2012) and Institute of Chemical
Engineering and Sciences, A*STAR of Singapore (2012

(2012-2015). He joined the Qingdao Institute of
Bioenergy and Bioprocess Technology, Chinese Academy of Sciences as professor since 2015. His
main research interests include he

heterogeneous catalysis and chemical technology for clean energy,
nanomaterials and nanocatalysts synthesis, etc.
Table of Contents
The research progress of Sn

Sn-based catalysts, including the research status of metallic tin catalysts,
Sn-based
based oxides, oxide
oxide-derived
oxid e-- tin catalysts, Sn-based sulfides, and the four strategies used
commonly to improve efficiency and selectivity are systematically summarized and discussed.
Carbon
arbon dioxide, electrochemical reduction, Sn ：Review
Sn-based catalyst, electrocatalysis：
Feng Chenga, b, #, Xinxin Zhangb, c, #, Kaiwen Mub, c, Xin Mab, Mingyang Jiaob, Zhiheng Wangb, c,
Paphada Limpachanangkuld, Benjapon Chalermsinsuwand, Ying Gaoa, Yunhui Lia, *, Zhipeng Chenb,
*
, Licheng Liub, e, f, *
Recent progress of Sn-

Sn-based
Sn -based
based derivative cat
catalysts for electrochemical reduction of CO2

Accepted Article

Khu CO2 Cheng 2020

Uploaded by

Document Information

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Khu CO2 Cheng 2020

Uploaded by

Copyright:

Available Formats

Recent progress of Sn-based derivative catalysts for electrochemical reduction of CO2

Keywords: carbon dioxide, electrochemica

This article is protected by copyright. All rights reserved

This article is protected by copyright. All rights reserved

The electrochemical reduction reaction of carbon dioxi

Among these high-

electron transfer reaction that easily occur

Therefore, it is considered to be an economically feasible, simple and effective method.[7]

This article is protected by copyright. All rights reserved

non-toxic, suitable for large-scale apply.[13] In the field of electrocatalysis, the

size,[1a, 14] morphology[[15

performance. This article reviews the research progress of Sn

Sn-based oxides,[15b, 16b, 16c, 17] oxide-derived tin catalysts,[12]

perspectives on the further research direct

2.1 Fundamental for CO2RR

chamber, anode chamber and ion

This article is protected by copyright. All rights reserved

(i.e., -1.9 V vs. NHE) is required in this process.[21]

multi-carbon products (CH3OH, C2H4...).[23] With the participation of H+, the

to solving the problems in CO2RR.

proton/electron reaction pathway, resulting in the formation of multi-carbon products such as

CH3OH and C2H4.

This article is protected by copyright. All rights reserved

faradaic efficiency, turnover frequency, etc.[18]

(1)) Current density ((j

electrode (A)) is defined as current density ((j).

(2) Overpotential ((𝜂

electron transfer to carbon dioxide molecule, electric quant

(3) Faradaic Efficiency (FE

F,, 96485 C mol−1).

(4) Turnover Frequency (TOF)

2.2 Mechanism research progress of Sn

situ/operando characterization techniques combined with density functional theory ((DFT)

2.2.1 Operando characterization techniques

connected with the

of the interfacial spectral characterization or evaluation.[28]

synergistic effect betw

IRRAS) or internal reflection (ATR

This article is protected by copyright. All rights reserved

intermediate in the CO2RR. Zheng et al.[31] designed a two-dimension ultrathin Pd nanosheets

for Pd catalysts. Although in

reaction mechanism of tin

in situ XPS, XAS and Raman.

2.2.2 DFT calculation

to the electronic structure of the catalysts.

This article is protected by copyright. All rights reserved

step was protonation process in which hydrog

According to the energy

free energy to form OCHO* intermediate was significantl

surface.. As shown in Figure 2e-f, the SnS/Aminated-C composite catalyst demonstrates

This article is protected by copyright. All rights reserved

reveal the reaction mechanism, but also help to down

CO2RR, which leads to a diffe

electrocatalytic behavior of different intermetallic phases toward CO2RR of Au-Sn bimetal

(Figure 3a). The reasonable intermetallic phase demonstrated the lowest

overpotential for CO2 reduction. Unde

This article is protected by copyright. All rights reserved

strategy for the improvement of the catalytic performance of Sn

electron transport by introducing conductive materials.

reduced to formic acid under lower over

promotes the improvement of the catalyst performance.

This article is protected by copyright. All rights reserved

electrochemical performance of the Cu/SnOx hetero structured nanoparticles coated on carbon

HCOOH in FE of 48% (Figure 4e-f).