Electrocatalytic CO2 Reduction to Alcohols with High Selectivity over a Two-Dimensional Fe2P2S6 Nanosheet

Article abstract of DOI:10.1021/acscatal.9b03180

Electrochemical conversion of CO₂ into alcohols provides an attractive path toward achieving a carbon-neutral cycle, while its efficiency is challenged by identifying active electrocatalysts for the CO₂ reduction reaction (CO₂RR). In this work, we report the Fe₂P₂S₆ nanosheet acts as an efficient CO₂RR electrocatalytst toward highly selective hydrogenation of CO₂ to alcohols. This catalyst is capable of achieving a high total Faradaic efficiency (FE_{methanol+ethanol}) of 88.3%, with a FE_methanol up to 65.2% at -0.20 V vs the reversible hydrogen electrode in 0.5 M KHCO₃ solution, much higher than most reported CO₂RR electrocatalysts. Density functional theory calculations indicate that Fe atom on the Fe₂P₂S₆ surface can be regared as the active site for alcohol formation.

Full text of DOI:10.1021/acscatal.9b03180

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Letter
Electrocatalytic CO2 Reduction to Alcohols with High
Selectivity over Two-Dimensional Fe2P2S6 Nanosheet
Lei Ji, Le Chang, Ya Zhang, Shiyong Mou, Ting Wang, Yonglan Luo, Zhiming M. Wang, and Xuping Sun
ACS Catal., Just Accepted Manuscript • DOI: 10.1021/acscatal.9b03180 • Publication Date (Web): 27 Sep 2019
Downloaded from pubs.acs.org on September 28, 2019
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ACS Catalysis
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Electrocatalytic CO2 Reduction to Alcohols with High
Selectivity over Two-Dimensional Fe2P2S6 Nanosheet
Lei Ji,†,§,# Le Chang,†,# Ya Zhang,†,§ Shiyong Mou,† Ting Wang,⊥,† Yonglan Luo,*,⊥ Zhiming Wang,†
and Xuping Sun*,†
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†Institute of Fundamental and Frontier Sciences, University of Electronic Science and Technology of China, Chengdu
§
610054, Sichuan, China, College of Chemistry, Sichuan University, Chengdu 610064, Sichuan, China, and ⊥ Chemical
Synthesis and Pollution Control Key Laboratory of Sichuan Province, College of Chemistry and Chemical Engineering,
China West Normal University, Nanchong 637002, Sichuan, China
ABSTRACT: Electrochemical conversion of CO2 into alcohols provides an attractive path toward achieving a carbon-neutral
cycle, while its efficiency is challenged by identifying active electrocatalysts for the CO2 reduction reaction (CO2RR). In this work,
we report Fe2P2S6 nanosheet acts as an efficient CO2RR electrocatalytst toward highly selective hydrogenation of CO2 to alcohols.
This catalyst is capable of achieving a high total Faradaic efficiency (FEmethanol + ethanol) of 88.3%, with a FEmethanol up to 65.2% at
−0.20 V vs. reversible hydrogen electrode in 0.5 M KHCO3 solution, much higher than most reported CO2RR electrocatalysts.
Density functional theory calculations indicate that Fe atom on the Fe2P2S6 surface can be regared as the active site for alcohol
formation.
KEYWORDS: Fe2P2S6 nanosheet, CO2 reduction reaction, electrocatalysts, alcohols, density functional theory
Here, we focus our attention on Fe2P2S6 nanosheet as a 2D
catalyst toward highly selective hydrogenation of CO2 to
INTRODUCTION
alcohols. At −0.20 V vs. reversible hydrogen electrode (RHE),
this catalyst attains a total FEmethanol + ethanol of 88.3% with a
high FEmethanol up to 65.2% in 0.5 M KHCO3, outperforming
most reported CO2RR electrocatalysts. It also exhibits strong
electrochemical stability with a slight deterioration during
30-h continuous electrocatalysis. Density functional theory
(DFT) calculations reveal that Fe atom acts as favorable
CO2RR active site and the thermodynamically favored process
promotes methanol production rather than ethanol production.
Over the past few decades, the overcombustion of fossil
fuels emits large amount of CO2 to the atmosphere, causing
serious global concerns.1,2 Electrocatalytic conversion of CO2
to valuable chemicals has been an attractive route to fix the
issue of growing energy demand and environmental
problems.3−6 CO2 can be electrochemically converted into
gaseous carbon products (CO,7−11 CH4,12−14 and C2H415−17) and
liquids like HCOOH18,19 and alcohols.20−26 However, the
electroreduction of CO2 to alcohols suffers from intricate six
or more electron/proton coupling steps and sluggish kinetics,
and thus it is highly urgent to identify efficient electrocatalysts
for CO2 reduction reaction (CO2RR) toward selective
production of alcohols.
RESULTS AND DISCUSSION
Figure 1a shows the whole fabrication process of Fe2P2S6
nanosheet (see Supporting Information for preparative details).
X-ray diffraction (XRD) patterns for the samples before and
after exfoliation are displayed in Figure 1b. It can be observed
that all the peaks are compatible with the JCPDF pattern (No.
74-1501) after exfoliation treatment, indicating the
crystallinity is preserved in the Fe2P2S6 nanosheet. Energy
dispersive X-ray spectrum (Figure S1) and inductively
coupled plasma mass spectrometry analysis both show that
atomic ratio for Fe/P/S of the sample is nearly 1:1:3. Besides,
the relative intensity of the peaks is weakened after
exfoliation, which comes from the different orientations of
Fe2P2S6 before and after exfoliation treatment.35,36 The
scanning electron microscopy (SEM) image (Figure S2a)
reveals that bulk Fe2P2S6 is flat with sizes of 20−40 μm. As
shown in Figure S2b, Fe2P2S6 owns dense layer structure from
the edge position. Transmission electron microscopy (TEM)
image for the exfoliated Fe2P2S6 reveals a sheet-shaped
structure (Figure 1c) confirming the formation of nanosheet
after exfoliation. High-resolution TEM (HRTEM) image for
Among alcohols, methanol and ethanol as hydrogen carriers
are widely used to feed the direct alcohols fuel cells because of
easy storage and rather high mass energy density (methanol:
6.1 kWh kg−1; ethanol: 8.0 kWh kg−1).27−29 Encouragingly,
some recent progress has been made to design and develop
CO2RR electrocatalysts for methanol and/or ethanol
production in aqueous media.21,30−34 Zhang et al. synthesized
hierarchical Pd/SnO2 nanosheets with a Faradaic efficiency for
methanol (FEmethanol) of 54.8±2%.21 Lu group reported several
noble metal-containing CO2RR electrocatalysts, including
[PYD]@Pd (FEmethanol
: :
35%),30 [PYD]@Cu-Pt (FEmethanol
37%),31 and [PYD]@Cu-Pd (FEethanol: 12±1%).32 Cu nanowire
array is also active for CO2-to-ethanol conversion but with a
low FEethanol of 5.0%,33 and Cu4Zn catalyst gives a much
higher FEethanol of 29.1%.34 Given that Fe is the cheapest and
one of the most abundant transition metals, Fe-based material
would offer us a most economical CO2RR electrocatalyst for
alcohol production, which however has rarely been explored.
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Fe2P2S6 nanosheet shows that interplanar spacing is 0.293 nm
corresponding with the (130) plane of Fe2P2S6, as shown in
Figure 1d. Atomic force microscopic (AFM) image manifests
that the average thickness of the exfoliated Fe2P2S6 nanosheet
is about 1.3 nm (Figure 1e). All these above characterizations
reveal that the successful synthesis of Fe2P2S6 nanosheet by
liquid exfoliation of bulk counterpart.
Page 2 of 6
respectively, corresponding to P–S bonds in P2S6 unit.39 The
peak at 134.5 eV is ascribed to the P–P bond.39 For the region
of S 2p (Figure 2d), only a pair of peaks are found, confirming
only one form of sulfur exists in the Fe2P2S6, which consistent
with crystal structure.
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Figure 3. (a) LSV curves of Fe2P2S6 nanosheet/CP. (b)
Chronoamperometry curves. (c) FEs of CO2RR products on
Fe2P2S6 nanosheet/CP at different potentials. (d) 1H NMR spectra
of 12C methanol standard sample and the electrolysis product
using 13CO2 as feeding gas.
We evaluated the catalytic CO2RR performance of the
Fe2P2S6 nanosheet using a three-electrode system. Figure 3a
presents linear sweep voltammetry (LSV) curves over Fe2P2S6
nanosheet/CP in Ar- and CO2-saturated electrolyte solution. A
higher cathodic current density can be clearly seen in
CO2-saturated 0.5 M KHCO3, revealing occurrence of CO2RR.
Thus, we choose the potential window from −0.20 to −0.50 V
for CO2RR by the LSV curves. As depicted in Figure 3b, the
current density begins high and falls to a steady state, which
may be attributed to the decrease in local concentration of CO2
and H+ near working electrode surface and double layer
charging.40−43 The steady current densities at a series of
applied potentials suggest good electrochemical stability of
Fe2P2S6 during CO2RR tests. On-line gas chromatography
(GC) and headspace GC (HS-GC) analyses were performed to
identify and quantify the reduction products (Figure S3 and
S4). Figure 3c shows FEs at different working potentials. As
observed, no H2 was produced and the FE of alcohols achieves
Figure 1. (a) Schematic illustration of the procedures to fabricate
Fe2P2S6 nanosheets. (b) XRD patterns of bulk Fe2P2S6 and
Fe2P2S6 nanosheets. (c) TEM, (d) HRTEM and (e) AFM images
of Fe2P2S6 nanosheets.
the maximum value of 88.3% (FEmethanol: 65.2%; FEethanol
:
23.1%) at –0.20 V (Figure 3c). Of note, Fe2P2S6 nanosheet
compares favorably to the behaviors of bulk Fe2P2S6 (Figure
S5) and most reported CO2RR catalysts (Table S1).
1
Combining GC, H nuclear magnetic resonance (NMR) data
(Figure S6) and ion chromatography (IC) analysis (Figure S7),
it is safely to conclude that electrocatalytic CO2RR over
Fe2P2S6 nanosheet only produces methanol, ethanol, and H2
without the formation of HCOOH, CH4, and CO.
Figure 2. (a) XPS survey spectrum of Fe2P2S6 nanosheet. XPS
spectra for Fe2P2S6 nanosheet in regions of (b) Fe 2p, (c) P 2p,
and S 2p.
Control experiments were performed to confirm that
methanol and ethanol were indeed generated by
electrochemical reduction of CO2 over Fe2P2S6 nanosheet. In
Ar-saturated 0.5 M KHCO3, there is no methanol and ethanol
at different potentials (Figure S8a). Also note that we failed to
detect methanol and ethanol when no potential was applied to
CO2-saturated electrolyte (Figure S8b). Isotope labeled 13CO2
was also used as feeding gas to trace the origin of carbon
source. As we can see in Figure 3d, the incorporation of 13C
X-ray photoelectron spectroscopy (XPS) survey spectrum of
Fe2P2S6 is presented in Figure 2a, which evidences the
presence of Fe, P, and S elements as well as O and C elements
arising from surface oxidation/contamination.37 As indicated
by Fe 2p region in Figure 2b, the peaks can be fitted at 709.5
and 722.8 eV corresponding to 2p3/2 and 2p1/2 of Fe2+.38
Another two peaks at 713.9 and 729.4 eV reveal the existence
of Fe3+.38 The spectra of P 2p (Figure 2c) exhibits binding
energies at 133.1 and 133.9 eV attributed to P 2p3/2 and P 2p1/2,
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ACS Catalysis
label into methanol was proved by the peak splitting shown in
step (PDS) is *HCOH→*H2COH, with a uphill free energy
change of 0.36 eV. On the black line pathway, the value of
PDS is 0.22 eV, occurring at the step of *H3CO→CH3OH. As
for the pathway to produce C2H5OH, the PDS is rather high for
the first step of *CO→2(*CO), with an uphill free energy
change of 0.35 eV. Although the reaction goes spontaneously
after the second CO molecule adsorbed, the first step hinders
such reaction pathway producing C2H5OH. Density of States
(DOS) of the C-2p orbitals of all the steps during the reduction
process to produce CH3OH are analyzed, as shown in Figure
4c. There is a distinct PDOS peak locating around −6.00 eV,
splitting into several small peaks and shifting to lower energy
levels while the first H appears. H atom promotes even
distribution of the electronic state of C atom, and the
corresponding △G is −1.90 eV. Furthermore, the PDOS peaks
increase in strength obviously with the second H adsorbed,
agreeing well with the relatively large changes in △G (−1.18
eV). It should be noted that the distinct peak of *OCH3 is
similar with the state of *CO, with strength increased and
energetic more stable (locating around −9.37 eV), indicating
the electronic state of C atom has reached a relatively stable
state. Detailed reaction energy profiles of Fe2P2S6 nanosheet to
convert CO2 to alcohols rather than HCOOH, CH4 are shown
in Figures S15−S18.
1H NMR, which provides direct evidence to manifest that
methanol in the system stemmed only from electrochemical
CO2RR over Fe2P2S6 nanosheet. Stability of catalyst is critical
to practical use. Fe2P2S6 nanosheet/CP shows no obvious
attenuation in yield during successive recycling tests at −0.50
V for 5 times (Figure S9). Furthermore, under sustained CO2
gas flow in cathode, there is a a slight decline in current
density during 30-h electrolysis at −0.50 V (Figure S10). The
Fe2P2S6 still maintains its nanosheet morphology (Figure S11)
after a long electrochemical measurement. And there is almost
no change in XPS spectra of Fe2P2S6 (Figure S12) after
long-term CO2RR electrolysis confirming it has strong
robustness against CO2RR electrolysis. After long-term
electrolysis, the yields of methanol and ethanol for Fe2P2S6
nanosheet/CP (Figure S13) shows no significant drop
compared with initial one, demonstrating that the excellent
eletrochemical stability of Fe2P2S6 nanosheet.
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CONCLUSION
In summary, Fe2P2S6 nanosheet is successfully developed as
a high-efficiency CO2RR electrocatalyst to convert CO2 to
alcohols. It achieves a FEmethanol
of 88.3% with a
+
ethanol
FEmethanol of 65.2% at −0.20 V vs. RHE in 0.5 M KHCO3.
Density functional theory calculations suggest that Fe atom on
the Fe2P2S6 surface serves as the active site for alcohols
formation. This work not only offers a cost-effective catalyst
for electrochemical conversion of CO2 to alcohols, but would
provide a novel outlook on future investigations of Fe-based
nanomaterials as advanced CO2RR catalysts for alcohols
product.
Figure 4. (a) Optimized geometry of CO2 over Fe2P2S6 surface
and corresponding charge distribution differences (red and blue
regions represent positive and negative charges, respectively). Fe,
bluish violet; P, pink; S, orange; O, red; C, gray. (b) Reaction
energy profile from DFT calculations for methanol and ethanol
production via CO2 reduction over Fe2P2S6 surface (the asterisk
symbol (*) denotes the adsorption site). (c) Density of states of p
orbital of C atom in each species during the process of
CO→CH3OH1.
ASSOCIATED CONTENT
Supporting Information
We conducted DFT calculations to gain further insight into
catalytic mechanism involved. The possible adsorption sites
including Fe, P, and S atoms are considered to locate the CO2
molecule (Figure S14). Full geometry optimization indicates
that CO2 tends to be strongly adsorbed at the bridge site above
two Fe atoms via end-on pattern with a binding energy of
−2.20 eV, which is significantly larger than the values for
other catalysts.44−46 As a result, the nearby S atom is pushed
outwards and bond to the carbon atom with the length of 1.83
Å, as shown in Figure 4a. Charge density differences are
shown in Figure 4b, where electrons accumulate at the region
between Fe and bottom O atoms, as well as between C and
adjacent S atoms, verifying the strong binding interactions
between CO2 and the electrocatalyst. The Löwdin charge
analysis shows that there is 0.49 e transfer from the surface to
CO2, indicating that the Fe atom on the surface donate
electrons to CO2 molecule. Subsequently, as shown in Figure
4b, the adsorbed CO2 can be feasibly reduced during the
hydrogenation process, indicated by the general downhill
profile of the Gibbs free energy change (△G). Three different
pathways are compared to verify the selectivity of the catalyst,
including the production of CH3OH molecule in two different
configurations and C2H5OH (Table S2). As for the reduction
process represented by the red line, the potential determining
1
Experimental details; H NMR and XPS spectra; SEM and TEM
images; energy dispersive X-ray, GC and IC data; calibration and
chronopotentiometry curves; yields and FEs; active sites; reaction
energy profiles; Tables S1 and S2. This material is available free
of charge via the Internet at http://pubs.acs.org.
AUTHOR INFORMATION
Corresponding Author
*E-mail: luoylcwnu@hotmail.com (Y.L.); xpsun@uestc.edu.cn
(X.S.)
#L.J. and L.C. contributed equally to this work
Notes
The authors declare no competing financial interest.
REFERENCES
(1)
Appel, A. M.; Bercaw, J. E.; Bocarsly, A. B.; Dobbek, H.;
DuBois, D. L.; Dupuis, M.; Ferry, J. G.; Fujita, E.; Hille, R.;
Kenis, P. J.; Kerfeld, C. A.; Morris, R. H.; Peden, C. H.;
Portis, A. R.; Ragsdale, S. W.; Rauchfuss, T. B.; Reek, J. N.;
Seefeldt, L. C.; Thauer, R. K.; Waldrop, G. L. Frontiers,
Opportunities, and Challenges in Biochemical and Chemical
Catalysis of CO2 Fixation. Chem. Rev. 2013, 113, 6621−6658.
ACS Paragon Plus Environment

ACS Catalysis
Page 4 of 6
(2)
Aresta, M.; Dibenedetto, A.; Angelini, A. Catalysis for the
Confined in Graphene Toward High-Efficiency Carbon
Dioxide Electroreduction. Nat. Commun. 2016, 7, 12697.
Jiangꢀ, K.; Sandberg, R. B.; Akey, A. J.; Liu, X.; Bell, D. C.;
Nørskov, J. K.; Chan, K.; Wang, H. Metal Ion Cycling of Cu
Foil for Selective C–C Coupling in Electrochemical CO2
Reduction. Nat. Catal. 2018, 1, 111–119.
Zhang, W.; Qin, Q.; Dai, L.; Qin, R.; Zhao, X.; Chen, X.; Ou,
D.; Chen, J.; Chuong, T.; Wu, B.; Zheng, N. Electrochemical
Reduction of Carbon Dioxide to Methanol on Hierarchical
Pd/SnO2 Nanosheets with Abundant Pd–O–Sn Interfaces.
Angew. Chem. Int. Ed. 2018, 57, 9475–9479.
Zhuang, T.-T.; Liang, Z.-Q.; Seifitokaldani, A.; Li, Y.; Lunaꢀ,
P. D.; Burdyny, T.; Che, F.; Meng, F.; Min, Y.;
Quintero-Bermudez, R.; Dinh, C. T.; Pang, Y.; Zhong, M.;
Zhang, B.; Li, J.; Chen, P.-N.; Zhengꢀ, X.-L.; Liang, H.; Ge,
W.-N.; Ye, B.-J.; Sinton, D.; Yu, S.-H.; Sargent, E. H.
Steering Post-C–C Coupling Selectivity Enables High
Efficiency Electroreduction of Carbon Dioxide to
Multi-Carbon Alcohols. Nat. Catal. 2018, 1, 421–428.
Kim, D.; Kleyd, C. S.; Li, Y.; Yang, P. Copper Nanoparticle
Ensembles for Selective Electroreduction of CO2 to C2–C3
Products. Proc. Natl. Acad. Sci. U. S. A. 2017, 114,
10560–10565.
Morales-Guioꢀ, C. G.; Cave, E. R.; Nitopi, S. A.; Feaster, J. T.;
Wang, L.; Kuhl, K. P.; Jackson, A.; Johnson, N. C.; Abram,
D. N.; Hatsukade, T.; Hahn, C.; Jaramillo, T. F. Improved
CO2 Reduction Activity towards C2+ Alcohols on a Tandem
Gold on Copper Electrocatalyst. Nat. Catal. 2018, 1, 764–771.
Zheng, Y.; Vasileff, A.; Zhou, X.; Jiao, Y.; Jaroniec, M.;
Qiao, S.-Z. Understanding the Roadmap for Electrochemical
Reduction of CO2 to Multi-Carbon Oxygenates and
Hydrocarbons on Copper-Based Catalysts. J. Am. Chem. Soc.
2019, 141, 7646–7659.
Jiao, Y.; Zheng, Y.; Chen, P.; Jaroniec, M.; Qiao, S.-Z.
Molecular Scaffolding Strategy with Synergistic Active
Centers to Facilitate Electrocatalytic CO2 Reduction to
Hydrocarbon/Alcohol. J. Am. Chem. Soc. 2017, 139,
18093–18100.
Kakati, N.; Maiti, J.; Lee, S. H.; Jee, S. H.; Viswanathan, B.;
Yoon, Y. S. Anode Catalysts for Direct Methanol Fuel Cells
in Acidic Media: Do We Have Any Alternative for Pt or
Pt−Ru? Chem. Rev. 2014, 114, 12397–12429.
Sial, M. A. Z. G.; Dina, M. A. U.; Wang, X. Multimetallic
Nanosheets: Synthesis and Applications in Fuel Cells. Chem.
Soc. Rev. 2018, 47, 6175–6200.
Rousseau, S.; Coutanceau, C.; Lamy, C.; Léger, J.-M. Direct
Ethanol Fuel Cell (DEFC): Electrical Performances and
Reaction Products Distribution under Operating Conditions
with Different Platinum-Based Anodes. J. Power Sources
2006, 158, 18–24.
Valorization of Exhaust Carbon: From CO2 to Chemicals,
Materials, and Fuels. Technological Use of CO2. Chem. Rev.
2014, 114, 1709−1742.
1
2
3
4
5
6
7
8
(20)
(21)
(3)
(4)
Mahmood, A.; Guo, W.; Tabassum, H.; Zou, R.
Metal-Organic
Framework-Based
Nanomaterials
for
Electrocatalysis. Adv. Energy Mater. 2016, 6, 1600423.
Graciani, J.; Mudiyanselage, K.; Xu, F.; Baber, A. E.; Evans,
J.; Senanayake, S. D.; Stacchiola, D. J.; Liu, P.; Hrbek, J.;
Sanz, J. F.; Rodriguez, J. A. Highly Active Copper-Ceria and
Copper-Ceria-Titania Catalysts for Methanol Synthesis from
CO2. Science 2014, 345, 546−550.
Vasileff, A.; Xu, C.; Jiao, Y.; Zheng, Y.; Qiao, S.-Z. Surface
and Interface Engineering in Copper-Based Bimetallic
Materials for Selective CO2 Electroreduction. Chem 2018, 4,
1809–1831.
9
(22)
(5)
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
(6)
(7)
(8)
Duan, X.; Xu, J.; Wei, Z.; Ma, J.; Guo, S.; Wang, S.; Liu, H.;
Dou, S. Metal-Free Carbon Materials for CO2 Electrochemical
Reduction. Adv. Mater. 2017, 29, 1701784.
Lu, Q.; Rosen, J.; Zhou, Y.; Hutchings, G. S.; Kimmel, Y. C.;
Chen, J. G.; Jiao, F. A Selective and Efficient Electrocatalyst
for Carbon Dioxide Reduction. Nat. Commun. 2014, 5, 3242.
Lu, C.; Yang, J.; Wei, S.; Bi, S.; Xia, Y.; Chen, M.; Hou, Y.;
Qiu, M.; Yuan, C.; Su, Y.; Zhang, F.; Liang, H.; Zhuang, X.
Atomic Ni Anchored Covalent Triazine Framework as High
Effcient Electrocatalyst for Carbon Dioxide Conversion. Adv.
Funct. Mater. 2019, 29, 1806884.
Cao, L.; Raciti, D.; Li, C.; Livi, K. J. T.; Rottmann, P. F.;
Hemker, K. J.; Mueller, T.; Wang, C. Mechanistic Insights for
Low-Overpotential Electroreduction of CO2 to CO on Copper
Nanowires. ACS Catal. 2017, 7, 8578−8587.
Gu, J.; Hsu, C.-S.; Bai, L.; Chen, H.; Hu, X. Atomically
Dispersed Fe3+ Sites Catalyze Efficient CO2 Electroreduction
to CO. Science 2019, 364, 1091−1094.
Asadi, M.; Kim, K.; Liu, C.; Addepalli, A. V.; Abbasi, P.;
Yasaei, P.; Phillips, P.; Behranginia, A.; Cerrato, J. M.;
Haasch, R.; Zapol, P.; Kumar, B.; Klie, R. F.; Abiade, J.;
Curtiss, L. A.; Salehi-Khojin, A. Nanostructured Transition
Metal Dichalcogenide Electrocatalysts for CO2 Reduction in
Ionic Liquid. Science 2016, 353, 460−470.
(23)
(24)
(9)
(25)
(26)
(27)
(10)
(11)
(12)
(13)
Zhao, Z.; Peng, X.; Liu, X.; Sun, X.; Shi, J.; Han, L.; Lia, G.;
Luo, J. Efficient and Stable Electroreduction of CO2 to CH4 on
CuS Nanosheet Arrays. J. Mater. Chem.
A
2017, 5,
(28)
(29)
20239–20243.
Kuhl, K. P.; Hatsukade, T.; Cave, E. R.; Abram, D. N.;
Kibsgaard, J.; Jaramillo, T. F. Electrocatalytic Conversion of
Carbon Dioxide to Methane and Methanol on Transition
Metal Surfaces. J. Am. Chem. Soc. 2014, 136, 14107–14113.
Liu, X.; Yang, H.; He, J.; Liu, H.; Song, L.; Li, L.; Luo, J.
Highly Active, Durable Ultrathin MoTe2 Layers for the
Electroreduction of CO2 to CH4. Small 2018, 14, 1704049.
Luna, P. D.; Quintero-Bermudez, R.; Dinh, C.-T.; Rossꢀ, M.
B.; Bushuyev, O. S.; Todorović, P.; Regier, T.; Kelley, S. O.;
Yang, P.; Sargent, E. H. Catalyst Electro-Redeposition
Controls Morphology and Oxidation State for Selective
Carbon Dioxide Reduction. Nat. Catal. 2018, 1, 103–110.
Mistry, H.; Varela, A. S.; Bonifacio, C. S.; Zegkinoglou, I.;
Sinev, I.; Choi, Y.-W.; Kisslinge, K.; Stach, E. A.; Yang, J.
C.; Strasser, P.; Cuenya, B. R. Highly Selective
Plasma-Activated Copper Catalysts for Carbon Dioxide
Reduction To Ethylene. Nat. Commun. 2016, 7, 12123.
Wu, J.; Ma, S.; Sun, J.; Gold, J. I.; Tiwary, C.; Kim, B.; Zhu,
L.; Chopra, N.; Odeh, I. N.; Vajtai, R.; Yu, A. Z.; Luo, R.;
Lou, J.; Ding, G.; Kenis, P. J. A.; Ajayan, P. M. A Metal-Free
Electrocatalyst for Carbon Dioxide Reduction to
Multi-Carbon Hydrocarbons and Oxygenates. Nat. Commun.
2016, 7, 13869.
(14)
(15)
(30)
(31)
Yang, H.; Qin, S.; Wang, H.; Lu, J. Organically Doped
Palladium: A Highly Efficient Catalyst for Electroreduction of
CO2 to Methanol. Green Chem. 2015, 17, 5144–5148.
Yang, H.; Yue, Y.; Qin, S.; Wang, H.; Lu, J. Selective
Electrochemical Reduction of CO2 to Different Alcohol
Products by an Organically Doped Alloy Catalyst. Green
Chem. 2016, 18, 3216–3220.
(16)
(17)
(32)
Yang, H.; Qin, S.; Yue, Y.; Liu, L.; Wang, H.; Lu, J.
Entrapment of
a
Pyridine Derivative within
a
Copper–Palladium Alloy:
A
Bifunctional Catalyst for
Electrochemical Reduction of CO2 to Alcohols with Excellent
Selectivity and Reusability. Catal. Sci. Technol. 2016, 6,
6490–6494.
Ma, M.; Djanashvili, K.; Smith, W. A. Controllable
Hydrocarbon Formation from the Electrochemical Reduction
of CO2 over Cu Nanowire Arrays. Angew. Chem. Int. Ed.
2016, 55, 6680–6684.
Ren, D.; Ang, B. S.-H.; Yeo, B. S. Tuning the Selectivity of
Carbon Dioxide Electroreduction toward Ethanol on
Oxide-Derived CuxZn Catalysts. ACS Catal. 2016, 6,
8239–8247.
Cheng, Z.; Shifa, T. A.; Wang, F.; Gao, Y.; He, P.; Zhang, K.;
Jiang, C.; Liu, Q.; He, J. High-Yield Production of Monolayer
(33)
(34)
(35)
(18)
(19)
Gao, S.; Lin, Y.; Jiao, X.; Sun, Y.; Luo, Q.; Zhang, W.; Li, D.;
Yang, J.; Xie, Y. Partially Oxidized Atomic Cobalt Layers for
Carbon Dioxide Electroreduction to Liquid Fuel. Nature 2016,
529, 68–71.
Lei, F.; Liu, W.; Sun, Y.; Xu, J.; Liu, K.; Liang, L.; Yao, T.;
Pan, B.; Wei, S.; Xie, Y. Metallic Tin Quantum Sheets
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Page 5 of 6
ACS Catalysis
FePS3 Quantum Sheets via Chemical Exfoliation for Effcient
Photocatalytic Hydrogen Evolution. Adv. Mater. 2018, 30,
1707433.
1
2
3
4
5
6
7
8
9
(36)
Zhu, W.; Gan, W.; Muhammad, Z.; Wang, C.; Wu, C.; Liu,
H.; Liu, D.; Zhang, K.; He, Q.; Jiang, H.; Zheng, X.; Sun, Z.;
Chen, S.; Song, L. Exfoliation of Ultrathin FePS3 Layers as a
Promising Electrocatalyst for the Oxygen Evolution Reaction.
Chem. Commun. 2018, 54, 4481−4484.
Liu, T.; Liu, D.; Qu, F.; Wang, D.; Zhang, L.; Ge, R.; Hao, S.;
Ma, Y.; Du, G.; Asiri, A. M.; Chen, L.; Sun, X. Enhanced
Electrocatalysis for Energy-Efficient Hydrogen Production
over CoP Catalyst with Nonelectroactive Zn as a Promoter.
Adv. Energy Mater. 2017, 7, 1700020.
(37)
10
11
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16
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18
19
20
21
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23
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27
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53
54
55
56
57
58
59
60
(38)
(39)
Liu, K.; Peng, Z.; Wang, H.; Ren, Y.; Liu, D.; Li, J.; Tang, Y.;
Zhang, N. Fe3C@Fe/N Doped Graphene-Like Carbon Sheets
as
a Highly Efficient Catalyst in Al-Air Batteries. J.
Electrochem. Soc. 2017, 164, F475–F483.
Fan, C.-Y.; Zhang, X.-H.; Shi, Y.-H.; Xu, H.-Y.; Zhang, J.-P.;
Wu, X.-L. 2D Few-Layer Iron Phosphosulfide: A Self-Buffer
Heterophase Structure Induced by Irreversible Breakage of
P–S Bonds for High-Performance Lithium/Sodium Storage. J.
Mater. Chem. A 2019, 7, 1529–1538.
Qiu, W.; Xie, X.-Y.; Qiu, J.; Fang, W.-H.; Liang, R.; Ren, X.;
Ji, X.; Cui, G.; Asiri, A. M.; Cui, G.; Tang, B.; Sun, X.
High-Performance Artificial Nitrogen Fixation at Ambient
Conditions using a Metal-Free Electrocatalyst. Nat. Commun.
2018, 9, 3485.
Zhou, F.; Azofra, L. M.; Ali, M.; Kar, M.; Simonov, A. N.;
McDonnell-Worth, C.; Sun, C.; Zhang, X.; MacFarlane, D. R.
Electro-Synthesis of Ammonia from Nitrogen at Ambient
Temperature and Pressure in Ionic Liquids. Energy Environ.
Sci. 2017, 10, 2516–2520.
Ren, D.; Fong, J.; Yeo, B. S. The Effects of Currents and
Potentials on the Selectivities of copper toward Carbon
Dioxide Electroreduction. Nat. Commun. 2018, 9, 925.
Singh, M. R.; Kwon, Y.; Lum, Y.; Ager, III, J. W.; Bell, A. T.
Hydrolysis of Electrolyte Cations Enhances the
Electrochemical Reduction of CO2 over Ag and Cu. J. Am.
Chem. Soc. 2016, 138, 13006–13012.
Zhai, L.; Cui, C.; Zhao, Y.; Zhu, X.; Han, J.; Wang, H.; Ge, Q.
Titania-Modified Silver Electrocatalyst for Selective CO2
Reduction to CH3OH and CH4 from DFT Study. J. Phys.
Chem. C 2017, 121, 16275–16282.
Kumari, N.; Haider, M. A.; Agarwal, M.; Sinha, N.; Basu, S.
Role of Reduced CeO2(110) Surface for CO2 Reduction to CO
and Methanol. J. Phys. Chem. C 2016, 120, 16626–16635.
Mahdavifar, Z.; Abbasi, N. The Influence of Cu-Doping on
Aluminum Nitride, Silicon Carbide and Boron Nitride
Nanotubes’ Ability to Detect Carbon Dioxide; DFT Study.
Physica E 2014, 56, 268–276.
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Fe2P2S6 nanosheet acts as a 2D catalyst toward highly selective electroreduction of
CO2 to alcohols. In 0.5 M KHCO3 solution, this catalyst is capable of achieving a high
total Faradaic efficiency (FEmethanol + ethanol) of 88.3%, with a FEmethanol up to 65.2% at
−0.20 V vs. reversible hydrogen electrode, much higher than most reported CO2RR
electrocatalytst. Density functional theory calculations reveal that Fe atom on the
Fe2P2S6 surface serves as the active site for alcohol formation.
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