Highly Selective Electrochemical Reduction of CO2 to Alcohols on an FeP Nanoarray

Article abstract of DOI:10.1002/anie.201912836

Electrochemical reduction of CO₂ into various chemicals and fuels provides an attractive pathway for environmental and energy sustainability. It is now shown that a FeP nanoarray on Ti mesh (FeP NA/TM) acts as an efficient 3D catalyst electrode for the CO₂ reduction reaction to convert CO₂ into alcohols with high selectivity. In 0.5 m KHCO₃, such FeP NA/TM is capable of achieving a high Faradaic efficiency (FE_CH3OH) up to 80.2 %, with a total FE FECH3OH+C2H5OH of 94.3 % at ?0.20 V vs. reversible hydrogen electrode. Density functional theory calculations reveal that the FeP(211) surface significantly promotes the adsorption and reduction of CO₂ toward CH₃OH owing to the synergistic effect of two adjacent Fe atoms, and the potential-determining step is the hydrogenation process of *CO.

Full text of DOI:10.1002/anie.201912836

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Accepted Article
Title: Highly Selective Electrochemical Reduction of CO2 to Alcohols
on FeP Nanoarray
Authors: Xuping Sun
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201912836
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COMMUNICATION
Highly Selective Electrochemical Reduction of CO2 to Alcohols
on FeP Nanoarray
Lei Ji,†[a,b] Lei Li,†[c] Xuqiang Ji,†[a] Ya Zhang,[a,b] Shiyong Mou,[a] Tongwei Wu,[a] Qian Liu,[a] Baihai Li,[c]
Xiaojuan Zhu,[a,d] Yonglan Luo,[d] Xifeng Shi,[e] Abdullah M. Asiri,[f] and Xuping Sun*[a]
Abstract: Electrochemical reduction of CO2 into various chemicals
and fuels provides an attractive pathway for environmental and
energy sustainability. In this communication, we report on our recent
experimental finding that FeP nanoarray on Ti mesh (FeP NA/TM)
acts as an efficient 3D catalyst electrode for the CO2 reduction
reaction to convert CO2 to alcohols with high selectivity. In 0.5 M
KHCO3, such FeP NA/TM is capable of achieving a high Faradaic
efficiency (FECH3OH) up to 80.2%, with a total FECH3OH+C2H5OH of 94.3%
at −0.20 V vs. reversible hydrogen electrode. Density functional
theory calculations reveal that the FeP(211) surface significantly
promotes the adsorption and reduction of CO2 toward CH3OH due to
the synergistic effect of two adjacent Fe atoms and the potential-
determining step is the hydrogenation process of *CO.
products. In this regard, it is needed to develop highly selective
and efficient electrocatalysts for CO2RR.
Fe is the cheapest and one of the most abundant of all
transition metals[22] and thus may hold great promise as a low-
cost catalyst material for large-scale uses. Iron macrocyclic
complexes represent one of the most extensively researched
categories of molecular catalysts for selective CO2 reduction to
CO.[23] Because of the synthetic issues of such complexes, it is
challenging to effectively immobilize them onto electrodes for
practical application, which can be avoided by heterogeneous
alternatives.[24−27] Porous Fe3N single crystal was reported to
yield CO with a selectivity of 90%.[24] Tour and co-workers
developed atomic iron dispersed on nitrogen-doped graphene
for CO2RR with a FE for CO of 80%.[25] Singly-dispersed FeN5
active sites supported on N-doped graphene enables CO2-to-CO
conversion with a FE of ~97.0%.[26] Recent study suggests that
discrete Fe3+ ions coordinated to pyrrolic nitrogen atoms of the
N-doped carbon support have ultrahigh activity for CO2
electroreduction to CO.[27] Compared with CO, alcohols
possesse advantages of higher energy density and easier
storage at atmospheric pressure, and they are also widely used
to feed the direct alcohols fuel cells.[28–30] Therefore, it is highly
attractive but still remains a big challenge to achieve efficient
electrocatalytic CO2 reduction to alcohols with high selectivity.
In this communication, we report the direct utilization of FeP
nanoarray on Ti mesh (FeP NA/TM) as an efficient 3D catalyst
electrode to electrochemically convert CO2 to alcohols. In 0.5 M
KHCO3, the FeP NA/TM offers a high FECH3OH up to 80.2%, with
a total FECH3OH+C2H5OH of 94.3% at −0.20 V vs. reversible
hydrogen electrode (RHE). It also shows a remarkably high
The massive comsuption of fossil fuels has led to an escalation
in atmospheric CO2 concentrations and such CO2 emissions trap
solar energy within the Earth’s atmosphere, which are
responsible for global climate change.[1,2] To struggle against the
greenhouse effect, research efforts have been extensively made
to develop technologies for capturing CO2 and sequestering or
utilizing it. Several routes have been explored to transform CO2
into other carbon compounds so far, including chemical
reforming,[3–5]
photochemical,[6–9]
biological,[10–12]
and
electrochemical[13–17] methods. Among them, electrocatalytic
reduction has emerged as an attractive way to resolve
environmental and energy issues.[18–21] For most electrocatalysts,
however, the inertness of CO2 molecules and complex multi-
electron transfer steps involved in CO2 reduction reaction
(CO2RR) result in large thermodynamic barriers, slow kinetics
and low Faraday efficiency (FE) and selectivity toward specific
stability during 36
h continuous electrocatalysis. Density
functional theory (DFT) calculations reveal that the FeP(211)
surface significantly promotes the adsorption and reduction of
CO2 toward CH3OH due to the synergistic effect of two adjacent
Fe atoms and the hydrogenation process of *CO is the potential-
determining step (PDS) with a free energy of 0.76 eV.
[a]
L. Ji, Dr. X. Ji, Y. Zhang, S. Mou, T. Wu, Dr. Q. Liu, X. Zhu, Prof.
X. Sun Institute of Fundamental and Frontier Sciences, University
of Electronic Science and Technology of China, Chengdu 610054,
Sichuan (China)
FeP NA/TM was derived from Fe2O3 NA/TM via our well-
established topotactic conversion process.[31] The X-ray
diffraction (XRD) pattern (Figure S1) for the precursor scratched
from TM shows characteristic peaks of Fe2O3 (JCPDS No. 84-
0306). The scanning electron microscopy (SEM) image indicates
that the surface of TM is coated with Fe2O3 nanorod array
(Figure S2). Following phosphidation, the product presents
characteristic diffraction peaks indexed to the (011), (111), (202),
(211), (103), (212), (020), and (114) planes of FeP phase
(JCPDS No. 78-1443), as shown in Figure 1a. Note that the FeP
product well maintains the nanoarray feature (Figure 1b). As
shown in Figure 1c, the transmission electron microscopy (TEM)
image further indicates the nanorod nature of FeP. The high-
resolution TEM (HRTEM) image (Figure 1d) taken from one
single FeP nanorod reveals clear lattice fringes with an
interplanar distance of 0.18 nm corresponding to the (211) plane
of FeP. The energy dispersive X-ray (EDX) spectrum shows the
presence of Fe and P elements with the atomic ratio of nearly
1:1, as shown in Figure S3. The scanning TEM (STEM) and
corresponding EDX elemental mapping images (Figure 1e)
E-mail: xpsun@uestc.edu.cn
L. Ji, Y. Zhang
College of Chemistry, Sichuan University, Chengdu 610064,
Sichuan (China)
L. Li, Prof. B. Li
School of Materials and Energy, University of Electronic Science
and Technology of China, Chengdu 611731, Sichuan (China)
X. Zhu, Y. Luo
Chemical Synthesis and Pollution Control Key Laboratory of
Sichuan Province, College of Chemistry and Chemical
Engineering, China West Normal University, Nanchong 637002,
Sichuan (China)
[b]
[c]
[d]
[e]
[f]
Dr. X. Shi
College of Chemistry, Chemical Engineering and Materials
Science, Shandong Normal University, Jinan 250014, Shandong
(China)
Prof. A. M. Asiri
Chemistry Department, Faculty of Science & Center of Excellence
for Advanced Materials Research, King Abdulaziz University, P.O.
Box 80203, Jeddah 21589 (Saudi Arabia)
†These authors contributed equally to this work.
Supporting information for this article is given via a link at the end
of the document.
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10.1002/anie.201912836
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further confirm the uniform distribution of Fe and P elements. All
above results strongly support the successful preparation of FeP
NA/TM.
energies at 706.5 and 719.3 eV correspond to 2p3/2 and 2p1/2 in
FeP, respectively, and the two peaks at 710.6 and 724.1 eV are
ascribed to Fe-O.[33] The peaks at 713.9 and 727.8 eV are well
fitted with two shakeup satellites.[33] The P 2p region (Figure 2c)
shows two peaks at 128.9 and 129.7 eV assigned to P 2p3/2 and
2p1/2 in FeP and the P-O species stem from surface oxidation of
P in FeP after exposure to air.[32,33] In the O 1s region (Figure 2d),
the fitted peaks at 530.1, 531.4, and 532.6 eV are ascribed to
lattice O, adsorbed O from surface hydroxy and/or adsorbed
oxygen species, and O from the surface of absorbed H2O,
respectively.[34]
Figure 1. (a) XRD pattern for FeP scratched from TM. (b) SEM image for FeP
NA/TM. (c) TEM and (d) HRTEM images taken from FeP nanorod. (e) STEM
image of FeP nanorod and EDX elemental mapping of Fe and P.
Figure 3. (a) LSV curves of FeP NA/TM in Ar- or CO2-saturated 0.5 M KHCO3
solution. (b) Chronoamperometry curves of CO2RR over FeP NA/TM in 0.5 M
KHCO3 solution at different potentials (error bars represent the standard
deviation of five measurements). (c) FEs of CO2RR products on FeP NA/TM at
different potentials. (d) Chromatograms for Ar-saturated 0.5 M KHCO3 at
different potentials using HS-GC. (e) Chromatograms for CO2-saturated 0.5 M
KHCO3 with and without potential applied to the electrochemical cell. (f)
Alcohols yields and FEs on FeP NA/TM at applied potential –0.20 V for 5
times cycle measurements.
We evaluated the catalytic CO2RR performance of the FeP
NA/TM using a three-electrode system. The potentials for
CO2RR are all reported on a RHE scale. Figure 3a presents the
linear sweep voltammetry (LSV) curves for FeP NA/TM in Ar-
and CO2-saturated 0.5 M KHCO3. Obviously, a higher cathodic
current density can be clearly seen in CO2-saturated electrolyte
on FeP NA/TM, indicating the occurrence of CO2RR. According
to the polarization curves, the appropriate potential window for
electrocatalytic CO2RR ranges from −0.20 to −0.40 V. Figure 3b
shows the chronoamperometry curves at different applied
potentials, in which the steady current densities suggest good
electrochemical stability of FeP NA/TM during CO2RR tests. To
identify the CO2 reduction products, on-line gas chromatography
Figure 2. (a) XPS survey spectrum of FeP. XPS spectra in the (b) Fe 3d, (c) P
2p, and (d) O 1s regions for FeP.
The X-ray photoelectron spectroscopy (XPS) survey spectrum
for FeP (Figure 2a) shows the peaks of Fe and P with signals of
C and O elements due to contamination/surface oxidation of the
product.[32] In the Fe 2p spectra (Figure 2b), two binding
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10.1002/anie.201912836
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(GC) and headspace GC (HS-GC) analyses were performed to
quantify the gaseous and liquid products (Figure S4 and S5).
The FEs at various potentials is calculated and shown in Figure
3c, respectively. As observed, the FE of alcohols achieves the
maximum value of 94.3% (FECH3OH: 80.2%; FEC2H5OH: 14.1%) at
–0.20 V. Here, note that the value of CH3OH is higher than those
for Fe2P2S6 nanosheet (65.2%)[35] and other electrocatalysts
(see Table S1). It is worth while mentioning that no CO2RR
products were detected on Fe2O3 NA/TM within the investigated
potential window (Table S2).
hydrogenation process of *CH2OH to *CH3OH is an uphill
pathway with ΔG = 0.28 eV, and surprisingly the *CH3OH
desorption is exothermic process with ΔG = −0.26 eV. For this
case, it suggests that the hydrogenation of *CO to *COH is the
PDS with ΔG = 0.76 eV while the *COH desorption is difficult
because C atom in *COH is fixed by two adjacent Fe atoms. On
the other pathway, double *CO adsorption is considered and
results show that it is a downhill pathway, which is advantage to
form C2H5OH. However, the hydrogenation is difficult with ΔG =
1.33 eV, implying that the formation of double carbon (C2)
intermediate (*CO-*COH) is not preferable. Moreover, the next
hydrogenation is also difficult with ΔG = 1.20 eV. Then, the rest
Control experiments were performed to further confirm that
CH3OH and C2H5OH were indeed generated by electrochemical
reduction of CO2 over FeP NA/TM. In Ar-saturated 0.5 M KHCO3, hydrogenation steps are facile due to exothermic process or
there is no CH3OH and C2H5OH at different potentials (Figure
3d). CH3OH and C2H5OH were not detected when no potential
was applied to CO2-saturated electrolyte (Figure 3e). H nuclear
endothermic process consuming a small energy, while the entire
reaction processes were presented in Figure S11. The PDS for
C2H5OH pathway is much higher than that of the CH3OH
pathway, suggesting that Fe(211) surface more prefers to
produce CH3OH, which is consistent with experiment results.
Overall, the PDS for CH3OH production is *CO to *COH process
with ΔG = 0.76 eV, which is comparable with that on the well-
established Cu(211) with ΔG = 0.74 eV.[37]
1
magnetic resonance (NMR) data (Figure S6) prove the formation
of CH3OH and C2H5OH during CO2RR process. Isotope labeled
13CO2 was also used as feeding gas to trace the origin of carbon
source. As we can see in Figure S7, the incorporation of the 13C
1
label into CH3OH was proved by the peak splitting shown in H
NMR,[36] which provides direct evidence to show that CH3OH in
the system only originate from electrochemical CO2RR over the
FeP NA/TM. All results provide clear evidence to support that
alcohols product in the system only stem from electrochemical
CO2RR over FeP NA/TM. Ion chromatography (IC) analysis
(Figure S8) also indicates that no HCOO– products formed over
FeP NA/TM at all potentials. Meanwhile it is safely to conclude
that electrocatalytic CO2RR over FeP NA/TM only produces
CH3OH, C2H5OH, and H2 without the formation of HCOO–, CH4,
and CO.
Stability is also a critical parameter of CO2RR performance for
practical applications. FeP NA/TM shows no obvious attenuation
in yield and FE during consecutive recycling tests at −0.20 V for
5 times (Figure 3f). Furthermore, under sustained CO2 gas flow
in cathode, 36-h electrolysis at a potential of −0.20 V only leads
to a slight decrease in current density (Figure S9). Compared
with the initial one, the yields of CH3OH and C2H5OH for FeP
NA/TM exhibits only 7% decrease (Figure S10) after long-term
electrolysis, indicating that high electrocatalytic activity for
CO2RR is maintained.
Figure 4. Free energy diagram for CO2RR process occurring on FeP(211).
Asterisk (*) denotes the adsorbed intermediate. The CH3OH and C2H5OH
synthesis reaction processes are drawn in blue and pink, respectively, with the
intermediated configurations.
DFT calculations were performed to gain further insight into
the catalytic mechanism. Based on the XRD and HRTEM data,
FeP(211) surface is considered. Firstly, CO2 molecule is
adsorbed on the two adjacent surface Fe atoms by side-on
coordination with a free energy change (ΔG) of −0.40 eV, and it
can be seen that carbon atom and one of oxygen atom in CO2
molecule interact with Fe atoms respectively, as shown in Figure
4. Bader charge analysis shows that CO2 molecule is transferred
into 0.69 e− from FeP(211) surface, implying that it is effectively
activated. Subsequently, the hydrogenation process of CO2 is
proceeded. The first hydrogenation of *CO2 prefers to take place
on the tilted oxygen atom (*COOH) with ΔG = −0.31 eV. Then,
the hydrogenation of *COOH should occur at the same oxygen
atom to form H2O molecule and *CO with ΔG = −0.31 eV, as
shown in Figure 4. Next, hydrogenation processes of *CO to
*COH and *COH to *CHOH are uphill pathway with ΔG = 0.76
and 0.70 eV respectively, and then *CHOH is hydrogenated to
*CH2OH with a downhill pathway of ΔG = −0.12 eV. The
To get a deep insight of the significant HER suppression on
the FeP(211) surface, ΔG*H on different reaction sites have been
calculated. As shown in Figure S12, four possible sites including
Fe-1, Fe-2, P-1 and P-2 were taken into consideration. The
calculated ΔG*H are 0.08, 0.16, 0.39 and 0.50 eV for Fe-1, Fe-2,
P-1 and P-2, respectively, as presented in Figure S13.
Obviously, the Fe sites are the most ideal active sites for HER
due to these values of ΔG*H are most close to zero. However,
the Fe sites might be occupied by CO2 molecule because of the
much stronger binding interactions with the ΔG*CO2 of −0.40 eV.
In addition, the rate for *CO formation reaches its maximum at
the onset potential for HER.[38] When the potential is below
−0.20 V, the decrease of *CO formation when the occurrence of
HER is attributed to the limited available sites, which further
affects the hydrogenation of CO2. In addition, the potential has
little effect on the chemical adsorption of CO, whereas the
electrochemical adsorption of H+ is determined by the potential
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value.[39] Therefore, when the potential is below –0.20 V, FEs of
CO2RR decrease and HER increase obviously.
Rauchfuss, J. N. H. Reek, L. C. Seefeldt, R. K. Thauer, G. L. Waldrop,
Chem. Rev. 2013, 113, 6621–6658.
[13] A. Vasileff, C. Xu, Y. Jiao, Y. Zheng, S.-Z. Qiao, Chem 2018, 4,
1809–1831.
In summary, FeP nanoarray is verified experimentally as a
superb electrocatalyst for CO2RR toward alcohols production
with high stability, capable of attaining a FECH3OH up to 80.2%
with a total FECH3OH+C2H5OH of 94.3% at −0.20 V vs. RHE.
Theoretical studies further suggest that the synergistic effect of
two adjacent Fe atoms on FeP(211) surface favors the
adsorption and reduction of CO2 to CH3OH and the potential-
determining step is the hydrogenation process of *CO with a free
energy of 0.76 eV. The whole fabrication process is cost-
effective and easy to scale-up. This feature, together with its
remarkable catalytic performances, promises its use as an
attractive earth-abundant catalyst material for CO2RR toward
alcohol electrosynthesis.
[14] L. Zhang, Z.-J. Zhao, J. Gong, Angew. Chem. Int. Ed. 2017, 56,
11326–11353.
[15] W. Zhang, Q. Qin, L. Dai, R. Qin, X. Zhao, X. Chen, D. Ou, J. Chen,
T. Chuong, B. Wu, N. Zheng, Angew. Chem. Int. Ed. 2018, 57, 9475–
9479.
[16] C. Chen, J. F. K. Kotyk, S. W. Sheehan, Chem 2018, 4, 2571–2586.
[17] J. Qiao, Y. Liu, F. Hong, J. Zhang, Chem. Soc. Rev. 2014, 43, 631–
675.
[18] E. V. Kondratenko, G. Mul, J. Baltrusaitis, G. O. Larrazábal, J. Pérez-
Ramírez, Energy Environ. Sci. 2013, 6, 3112–3135.
[19] D. Zhu, J. Liu, S. Qiao, Adv. Mater. 2016, 28, 3423–3452.
[20] X. Duan, J. Xu, Z. Wei, J. Ma, S. Guo, S. Wang, H. Liu, S. Dou, Adv.
Mater. 2017, 29, 1701784.
[21] H. Xie, T. Wang, J. Liang, Q. Li, S. Sun, Nano Today 2018, 21, 41–
54.
[22] P. Jiang, Q. Liu, Y. Liang, J. Tian, A. M. Asiri, X. Sun, Angew. Chem.
Int. Ed. 2014, 53, 12855–12859.
Acknowledgement
[23] K. Elouarzaki, V. Kannan, V. Jose, H. S. Sabharwal, J.-M. Lee, Adv.
Energy Mater. 2019, 9, 1900090.
This work was supported by the National Natural Science
Foundation of China (No. 21575137). We also appreciate Hui
Wang from the Analytical & Testing Center of Sichuan University
for her help with SEM characterization.
[24] F. Zhang, S. Xi, G. Lin, X. Hu, X. W. Lou, K. Xi, Adv. Mater. 2019, 31,
1806552.
[25] C. Zhang, S. Yang, J. Wu, M. Liu, S. Yazdi, M. Ren, J. Sha, J. Zhong,
K. Nie, A. S. Jalilov, Z. Li, H. Li, B. I. Yakobson, Q. Wu, E. Ringe, H.
Xu, P. M. Ajayan, J. M. Tour, Adv. Energy Mater. 2018, 8, 1703487.
[26] H. Zhang, J. Li, S. Xi, Y. Du, X. Hai, J. Wang, H. Xu, G. Wu, J. Zhang,
J. Lu, J. Wang, Angew. Chem. Int. Ed. 2019, DOI:
10.1002/ange.201906079.
Keywords: FeP • CO2 reduction reaction • electrocatalysts •
alcohols • density functional theory
[27] J. Gu, C.-S. Hsu, L. Bai, H. M. Chen, X. Hu, Science 2019, 364,
1091–1094.
[1] S. S. Myers, K. R. Wessells, I. Kloog, A. Zanobetti, J. Schwartz,
Lancet Glob. Health 2015, 3, e639–e645.
[28] N. Kakati, J. Maiti, S. H. Lee, S. H. Jee, B. Viswanathan, Y. S. Yoon,
Chem. Rev. 2014, 114, 12397–12429.
[2] D. R. Feldman, W. D. Collins, P. J. Gero, M. S. Torn, E. J. Mlawer, T.
R. Shippert, Nature 2015, 519, 339–343.
[29] M. A. Z. G. Sial, M. A. U. Dina, X. Wang, Chem. Soc. Rev. 2018, 47,
6175–6200.
[3] J. Graciani, K. Mudiyanselage, F. Xu, A. E. Baber, J. Evans, S. D.
Senanayake, D. J. Stacchiola, P. Liu, J. Hrbek, J. F. Sanz, J. A.
Rodriguez, Science 2014, 345, 546.
[30] F. Jia, X. Yu, L. Zhang, J. Power Sources 2014, 252, 85–89.
[31] J. Tian, Q. Liu, A. M. Asiri, X. Sun, J. Am. Chem. Soc. 2014, 136,
7587–7590.
[4] J. Ma, N. Sun, X. Zhang, N. Zhao, F. Xiao, W. Wei, Y. Sun, Catal.
Today 2009, 148, 221–231.
[32] T. Liu, D. Liu, F. Qu, D. Wang, L. Zhang, R. Ge, S. Hao, Y. Ma, G. Du,
A. M. Asiri, L. Chen, X. Sun, Adv. Energy Mater. 2017, 7, 1700020.
[33] X. Peng, A. M. Qasim, W. Jin, L. Wang, L. Hu, Y. Miao, W. Li, Y. Li, Z.
Liu, K. Huo, K. Wong, P. K. Chu, Nano Energy 2018, 53, 66–73.
[34] Z. Wang, H. Liu, R. Ge, X. Ren, J. Ren, D. Yang, L. Zhang, X. Sun,
ACS Catal. 2018, 8, 2236–2241.
[5] X. Pan, Z. Fan, W. Chen, Y. Ding, H. Luo, X. Bao, Nat. Mater. 2007,
6, 507.
[6] T. Ouyang, H.-H. Huang, J.-W. Wang, D.-C. Zhong, T.-B. Lu, Angew.
Chem. Int. Ed. 2017, 56, 738–743.
[7] X. Chang, T. Wang, P. Zhang, Y. Wei, J. Zhao, J. Gong, Angew.
Chem. Int. Ed. 2016, 55, 8840–8845.
[35] L. Ji, L. Chang, Y. Zhang, S. Mou, T. Wang, Y. Luo, Z. Wang, X. Sun,
ACS Catal. 2019, 9, 9721–9725.
[8] S. Sato, T. Morikawa, T. Kajino, O. Ishitani, Angew. Chem. Int. Ed.
2013, 52, 988–992.
[36] K. P. Kuhl, T. Hatsukade, E. R. Cave, D. N. Abram, J. Kibsgaard, T.
F. Jaramillo, J. Am. Chem. Soc. 2014, 136, 14107–14113.
[37] A. A. Peterson, F. Abild-Pedersen, F. Studt, J. Rossmeisl, J. K.
Nørskov, Energy Environ. Sci. 2010, 3, 1311–1315.
[38] J. Yang, J. Wei, W. Chen, Y. Chen, Chin. J. Chem. Phys. 2018, 31,
626−634.
[9] S. Sato, T. Morikawa, S. Saeki, T. Kajino, T. Motohiro, Angew. Chem.
Int. Ed. 2010, 49, 5101–5105.
[10] K. Schuchmann, V. Müller, Science 2013, 342, 1382–1385.
[11] M. Mondal, S. Khanra, O. N. Tiwari, K. Gayen, G. N. Halder, Environ.
Prog. Sustainable Energy 2016, 35, 1605–1615.
[12] A. M. Appel, J. E. Bercaw, A. B. Bocarsly, H. Dobbek, D. L. DuBois,
M. Dupuis, J. G. Ferry, E. Fujita, R. Hille, P. J. A. Kenis, C. A. Kerfeld,
R. H. Morris, C. H. F. Peden, A. R. Portis, S. W. Ragsdale, T. B.
[39] Z. Chen, W. Gao, W. Zheng, Q. Jiang, ChemSusChem 2018, 11,
1455–1459.
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COMMUNICATION
Lei Ji,†[a,b] Lei Li,†[c] Xuqiang Ji,†[a] Ya
Zhang,[a,b] Shiyong Mou,[a] Tongwei Wu,[a]
Qian Liu,[a] Baihai Li,[c] Xiaojuan Zhu,[a,d]
Yonglan Luo,[d] Xifeng Shi,[e] Abdullah M.
Asiri,[f] and Xuping Sun*[a]
Page No. – Page No.
FeP nanoarray on Ti mesh (FeP NA/TM) performs efficiently to electrocatalyze CO2
reduction to alcohols with a high Faradaic efficiency (FECH3OH) up to 80.2% and a
total FECH3OH+C2H5OH of 94.3% at −0.20 V vs. reversible hydrogen electrode. Density
functional theory calculations reveal that the FeP(211) surface significantly
promotes the adsorption and reduction of CO2 toward CH3OH due to the synergistic
effect of two adjacent Fe atoms and the potential-determining step is the
hydrogenation process of *CO.
Highly Selective Electrochemical
Reduction of CO2 to Alcohols on FeP
Nanoarray
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