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Nano Research 2022, 15(8): 7116-7123 https://doi.org/10.1007/s12274-022-4476-2
Research Article | Issue | Published: 02 June 2022

Rational design of copper-based single-atom alloy catalysts for electrochemical CO2 reduction

Show Author's Information Jian-Chao Jiang1,2,§,  Jun-Chi Chen2,§,  Meng-die Zhao1,  Qi Yu1( ),  Yang-Gang Wang2( ),  Jun Li2,3
School of Materials Science and Engineering, and Shaanxi Laboratory of Catalysis, Shaanxi University of Technology, Hanzhong 723001, China
Department of Chemistry and Guangdong Provincial Key Laboratory of Catalysis, Southern University of Science and Technology, Shenzhen 518055, China
Department of Chemistry and Key Laboratory of Organic Optoelectronics & Molecular Engineering of Ministry of Education, Tsinghua University, Beijing 100084, China

§ Jian-Chao Jiang and Jun-Chi Chen contributed equally to this work.

Keywords:
density functional theory, CO2 electrochemical reduction , Cu, single-atom alloy catalysts
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Electrocatalysts
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Jiang J-C, Chen J-C, Zhao M-d, et al. Rational design of copper-based single-atom alloy catalysts for electrochemical CO2 reduction. Nano Research, 2022, 15(8): 7116-7123. https://doi.org/10.1007/s12274-022-4476-2
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Abstract Full text Electronic supplementary material About this article

Electrochemical CO2-reduction reaction (CO2RR) is a promising way to alleviate energy crisis and excessive carbon emission. The Cu-based electrocatalysts have been considered for CO2RR to generate hydrocarbons and alcohols. However, the application of Cu electrocatalysts has been restricted by a high onset potential for CO2RR and low selectivity. In this study, we have designed a series of Cu-based single-atom alloy catalysts (SAAs), denoted as TM1/Cu (111), by doping isolated 3d-transition metal (TM) atom onto the Cu (111) surface. We theoretically evaluated their stability and investigated the activity and selectivity toward CO2RR. Compared to the pure Cu catalyst, the majority TM1/Cu (111) catalysts are more favorable for hydrogenating CO2 and can efficiently avoid the hydrogen-evolution reaction due to the strong binding of carbonaceous intermediates. Based on the density functional theory calculations, instead of the HCOOH or CO products, the initial hydrogenation of CO2 on SAAs would form the *CO intermediate, which could be further hydrogenated to produce methane. In addition, we have identified the bond angle of adsorbed *CO2 can describe the CO2 activation ability of TM1/Cu (111) and the binding energy of *OH can describe the CO2RR activity of TM1/Cu (111). We speculated that the V/Cu (111) can show the best activity and selectivity for CO2RR among all the 3d-TM-doped TM1/Cu (111). This work could provide a rational guide to the design of new type of single-atom catalysts for efficient CO2RR.


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About this article

Rational design of copper-based single-atom alloy catalysts for electrochemical CO2 reduction

Show Author's information Jian-Chao Jiang1,2,§, Jun-Chi Chen2,§, Meng-die Zhao1, Qi Yu1( ), Yang-Gang Wang2( ), Jun Li2,3
School of Materials Science and Engineering, and Shaanxi Laboratory of Catalysis, Shaanxi University of Technology, Hanzhong 723001, China
Department of Chemistry and Guangdong Provincial Key Laboratory of Catalysis, Southern University of Science and Technology, Shenzhen 518055, China
Department of Chemistry and Key Laboratory of Organic Optoelectronics & Molecular Engineering of Ministry of Education, Tsinghua University, Beijing 100084, China

§ Jian-Chao Jiang and Jun-Chi Chen contributed equally to this work.

Abstract

Electrochemical CO2-reduction reaction (CO2RR) is a promising way to alleviate energy crisis and excessive carbon emission. The Cu-based electrocatalysts have been considered for CO2RR to generate hydrocarbons and alcohols. However, the application of Cu electrocatalysts has been restricted by a high onset potential for CO2RR and low selectivity. In this study, we have designed a series of Cu-based single-atom alloy catalysts (SAAs), denoted as TM1/Cu (111), by doping isolated 3d-transition metal (TM) atom onto the Cu (111) surface. We theoretically evaluated their stability and investigated the activity and selectivity toward CO2RR. Compared to the pure Cu catalyst, the majority TM1/Cu (111) catalysts are more favorable for hydrogenating CO2 and can efficiently avoid the hydrogen-evolution reaction due to the strong binding of carbonaceous intermediates. Based on the density functional theory calculations, instead of the HCOOH or CO products, the initial hydrogenation of CO2 on SAAs would form the *CO intermediate, which could be further hydrogenated to produce methane. In addition, we have identified the bond angle of adsorbed *CO2 can describe the CO2 activation ability of TM1/Cu (111) and the binding energy of *OH can describe the CO2RR activity of TM1/Cu (111). We speculated that the V/Cu (111) can show the best activity and selectivity for CO2RR among all the 3d-TM-doped TM1/Cu (111). This work could provide a rational guide to the design of new type of single-atom catalysts for efficient CO2RR.

Keywords: density functional theory, CO2 electrochemical reduction , Cu, single-atom alloy catalysts

References(52)

1

Karl, T. R.; Trenberth, K. E. Modern global climate change. Science 2003, 302, 1719–1723.
DOI Google Scholar
2

Olah, G. A.; Prakash, G. K. S.; Goeppert, A. Anthropogenic chemical carbon cycle for a sustainable future. J. Am. Chem. Soc. 2011, 133, 12881–12898.
DOI Google Scholar
3

Kim, J.; Johnson, T. A.; Miller, J. E.; Stechel, E. B.; Maravelias, C. T. Fuel production from CO2 using solar-thermal energy: System level analysis. Energy Environ. Sci. 2012, 5, 8417–8429.
DOI Google Scholar
4

Li, Z. H.; Shi, R.; Zhao, J. Q.; Zhang, T. R. Ni-based catalysts derived from layered-double-hydroxide nanosheets for efficient photothermal CO2 reduction under flow-type system. Nano Res. 2021, 14, 4828–4832.
DOI Google Scholar
5

Jing, H. Y.; Zhu, P.; Zheng, X. B.; Zhang, Z. D.; Wang, D. S.; Li, Y. D. Theory-oriented screening and discovery of advanced energy transformation materials in electrocatalysis. Adv. Powder Mater. 2022, 1, 100013.
DOI Google Scholar
6

Meng, Y. C.; Kuang, S. Y.; Liu, H.; Fan, Q.; Ma, X. B.; Zhang, S. Recent advances in electrochemical CO2 reduction using copper-based catalysts. Acta Phys. Chim. Sin. 2021, 37, 2006034.
DOI Google Scholar
7

Wang, Y.; Zheng, X. B.; Wang, D. S. Design concept for electrocatalysts. Nano Res, 2022, 15, 1730–1752.
DOI Google Scholar
8

Chen, S. H.; Li, W. H.; Jiang, W. J.; Yang, J. R.; Zhu, J. X.; Wang, L. Q.; Ou, H. H.; Zhuang, Z. C.; Chen, M. Z.; Sun, X. H. et al. MOF encapsulating N-heterocyclic carbene-ligated copper single-atom site catalyst towards efficient methane electrosynthesis. Angew. Chem., Int. Ed. 2022, 134, e202114450.
DOI Google Scholar
9

Lu, Q.; Jiao, F. Electrochemical CO2 reduction: Electrocatalyst, reaction mechanism, and process engineering. Nano Energy 2016, 29, 439–456.
DOI Google Scholar
10

Sun, K.; Ji, Y. J.; Liu, Y. Y.; Wang, Z. J. Synergies between electronic and geometric effects of Mo-doped Au nanoparticles for effective CO2 electrochemical reduction. J. Mater. Chem. A 2020, 8, 12291–12295.
DOI Google Scholar
11

Sun, K.; Wu, L. N.; Qin, W.; Zhou, J. G.; Hu, Y. F.; Jiang, Z. H.; Shen, B. Z.; Wang, Z. J. Enhanced electrochemical reduction of CO2 to CO on Ag electrocatalysts with increased unoccupied density of states. J. Mater. Chem. A 2016, 4, 12616–12623.
DOI Google Scholar
12

Jiang, S. Y.; Liu, J. X.; Zhao, K.; Cui, D. D.; Liu, P. R.; Yin, H. J.; Al-Mamun, M.; Lowe, S. E.; Zhang, W. P.; Zhong, Y. L. et al. Ru(bpy)32+-sensitized {001} facets LiCoO2 nanosheets catalyzed CO2 reduction reaction with 100% carbonaceous products. Nano Res. 2022, 15, 1061–1068.
DOI Google Scholar
13

Gao, D. F.; Zhou, H.; Cai, F.; Wang, J. G.; Wang, G. X.; Bao, X. H. Pd-containing nanostructures for electrochemical CO2 reduction reaction. ACS Catal. 2018, 8, 1510–1519.
DOI Google Scholar
14

Cai, F.; Gao, D. F.; Zhou, H.; Wang, G. X.; He, T.; Gong, H. M.; Miao, S.; Yang, F.; Wang, J. G.; Bao, X. H. Electrochemical promotion of catalysis over Pd nanoparticles for CO2 reduction. Chem. Sci. 2017, 8, 2569–2573.
DOI Google Scholar
15

Nguyen, D. L. T.; Jee, M. S.; Won, D. H.; Oh, H. S.; Min, B. K.; Hwang, Y. J. Effect of halides on nanoporous Zn-based catalysts for highly efficient electroreduction of CO2 to CO. Catal Commun. 2018, 114, 109–113.
DOI Google Scholar
16

Xie, H.; Wang, T. Y.; Liang, J. S.; Li, Q.; Sun, S. H. Cu-based nanocatalysts for electrochemical reduction of CO2. Nano Today 2018, 21, 41–54.
DOI Google Scholar
17

Mou, S. Y.; Li, Y. H.; Yue, L. C.; Liang, J.; Luo, Y. L.; Liu, Q.; Li, T. S.; Lu, S. Y.; Asiri, A. M.; Xiong, X. L. et al. Cu2Sb decorated Cu nanowire arrays for selective electrocatalytic CO2 to CO conversion. Nano Res. 2021, 14, 2831–2836.
DOI Google Scholar
18
Hori, Y. Electrochemical CO2 reduction on metal electrodes. In Modern Aspects of Electrochemistry. Vayenas, C. G.; White, R. E.; Gamboa-Aldeco, M. E., Eds.; Springer: New York, 2008; pp 89–189.
19

Scholten, F.; Sinev, I.; Bernal, M.; Cuenya, B. R. Plasma-modified dendritic Cu catalyst for CO2 electroreduction. ACS Catal. 2019, 9, 5496–5502.
DOI Google Scholar
20

Niu, Z. Z.; Gao, F. Y.; Zhang, X. L.; Yang, P. P.; Liu, R.; Chi, L. P.; Wu, Z. Z.; Qin, S.; Yu, X. X.; Gao, M. R. Hierarchical copper with inherent hydrophobicity mitigates electrode flooding for high-rate CO2 electroreduction to multicarbon products. J. Am. Chem. Soc. 2021, 143, 8011–8021.
DOI Google Scholar
21

Chang, Y. B.; Zhang, C.; Lu, X. L.; Zhang, W.; Lu, T. B. Graphdiyene enables ultrafine Cu nanoparticles to selectively reduce CO2 to C2+ products. Nano Res. 2022, 15, 195–201.
DOI Google Scholar
22

Peterson, A. A.; Nørskov, J. K. Activity descriptors for CO2 electroreduction to methane on transition-metal catalysts. J. Phys. Chem. Lett. 2012, 3, 251–258.
DOI Google Scholar
23

Liu, J.; Cai, Y. M.; Song, R. B.; Ding, S. C.; Lyu, Z. Y.; Chang, Y. C.; Tian, H. Y.; Zhang, X.; Du, D.; Zhu, W. L. et al. Recent progress on single-atom catalysts for CO2 electroreduction. Mater. Today 2021, 48, 95–114.
DOI Google Scholar
24

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.
DOI Google Scholar
25

Nie, X. W.; Esopi, M. R.; Janik, M. J.; Asthagiri, A. Selectivity of CO2 reduction on copper electrodes: The role of the kinetics of elementary steps. Angew. Chem., Int. Ed. 2013, 52, 2459–2462.
DOI Google Scholar
26

Qiao, B. T.; Wang, A. Q.; Yang, X. F.; Allard, L. F.; Jiang, Z.; Cui, Y. T.; Liu, J. Y.; Li, J.; Zhang, T. Single-atom catalysis of CO oxidation using Pt1/FeOx. Nature Chem. 2011, 3, 634–641.
DOI Google Scholar
27

Li, X. G.; Bi, W. T.; Chen, M. L.; Sun, Y. X.; Ju, H. X.; Yan, W. S.; Zhu, J. F.; Wu, X. J.; Chu, W. S.; Wu, C. Z. et al. Exclusive Ni-N4 sites realize near-unity CO selectivity for electrochemical CO2 reduction. J. Am. Chem. Soc. 2017, 139, 14889–14892.
DOI Google Scholar
28

Wang, A. Q.; Li, J.; Zhang, T. Heterogeneous single-atom catalysis. Nat. Rev. Chem. 2018, 2, 65–81.
DOI Google Scholar
29

Liu, J. C.; Wang, Y. G.; Li, J. Toward rational design of oxide-supported single-atom catalysts: Atomic dispersion of gold on ceria. J. Am. Chem. Soc. 2017, 139, 6190–6199.
DOI Google Scholar
30

Rong, P.; Jiang, Y. F.; Wang, Q.; Gu, M.; Jiang, X. L.; Yu, Q. Photocatalytic degradation of methylene blue (MB) with Cu1-ZnO single atom catalysts on graphene-coated flexible substrates. J. Mater. Chem. A 2022, 10, 6231–6241.
DOI Google Scholar
31

Sun, T. T.; Xu, L. B.; Wang, D. S.; Li, Y. D. Metal organic frameworks derived single atom catalysts for electrocatalytic energy conversion. Nano Res. 2019, 12, 2067–2080.
DOI Google Scholar
32

Kyriakou, G.; Boucher, M. B.; Jewell, A. D.; Lewis, E. A.; Lawton, T. J.; Baber, A. E.; Tierney, H. L.; Flytzani-Stephanopoulos, M.; Sykes, E. C. H. Isolated metal atom geometries as a strategy for selective heterogeneous hydrogenations. Science 2012, 335, 1209–1212.
DOI Google Scholar
33

Qin, R. X.; Liu, P. X.; Fu, G.; Zheng, N. F. Strategies for stabilizing atomically dispersed metal catalysts. Small Methods 2018, 2, 1700286.
DOI Google Scholar
34

Hannagan, R. T.; Giannakakis, G.; Flytzani-Stephanopoulos, M.; Sykes, E. C. H. Single-atom alloy catalysis. Chem. Rev. 2020, 120, 12044–12088.
DOI Google Scholar
35

Watanabe, M.; Shibata, M.; Kato, A.; Azuma, M.; Sakata, T. Design of alloy electrocatalysts for CO2 reduction: III. The selective and reversible reduction of on Cu alloy electrodes. J. Electrochem. Soc. 1991, 138, 3382–3389.
DOI Google Scholar
36

Wang, C. Q.; Cao, M. L.; Jiang, X. X.; Wang, M. K.; Shen, Y. A catalyst based on copper-cadmium bimetal for electrochemical reduction of CO2 to CO with high Faradaic efficiency. Electrochim. Acta 2018, 271, 544–550.
DOI Google Scholar
37

Hirunsit, P.; Soodsawang, W.; Limtrakul, J. CO2 Electrochemical reduction to methane and methanol on copper-based alloys: Theoretical insight. J. Phys. Chem. C. 2015, 119, 8238–8249.
DOI Google Scholar
38

Wang, Z. J.; Yuan, Q.; Shan, J. J.; Jiang, Z. H.; Xu, P.; Hu, Y. F.; Zhou, J. G.; Wu, L. N.; Niu, Z. Z.; Sun, J. M. et al. Highly selective electrocatalytic reduction of CO2 into methane on Cu-Bi nanoalloys. J. Phys. Chem. Lett. 2020, 11, 7261–7266.
DOI Google Scholar
39

Kresse, G.; Furthmüller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 1996, 54, 11169–11186.
DOI Google Scholar
40

Kresse, G.; Furthmüller, J. Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. Comput. Mater. Sci. 1996, 6, 15–50.
DOI Google Scholar
41

Blöchl, P. E. Projector augmented-wave method. Phys. Rev. B 1994, 50, 17953–17979.
DOI Google Scholar
42

Kresse, G.; Joubert, D. From ultrasoft pseudopotentials to the projector augmented-wave method. Phys. Rev. B 1999, 59, 1758–1775.
DOI Google Scholar
43

Perdew, J. P.; Burke, K.; Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 1996, 77, 3865–3868.
DOI Google Scholar
44

Monkhorst, H. J.; Pack, J. D. Special points for Brillouin-zone integrations. Phys. Rev. B 1976, 13, 5188–5192.
DOI Google Scholar
45

Nørskov, J. K.; Rossmeisl, J.; Logadottir, A.; Lindqvist, L.; Kitchin, J. R.; Bligaard, T.; Jónsson, H. Origin of the overpotential for oxygen reduction at a fuel-cell cathode. J. Phys. Chem. B 2004, 108, 17886–17892.
DOI Google Scholar
46

Zhuang, T. T.; Liang, Z. Q.; Seifitokaldani, A.; Li, Y.; De Luna, P.; Burdyny, T.; Che, F. L.; Meng, F.; Min, Y. M.; Quintero-Bermudez, R. et al. Steering post-C–C coupling selectivity enables high efficiency electroreduction of carbon dioxide to multi-carbon alcohols. Nat. Catal. 2018, 1, 421–428.
DOI Google Scholar
47

Shi, J. J.; Owen, C. J.; Ngan, H. T.; Qin, S. Y.; Mehar, V.; Sautet, P.; Weaver, J. F. Formation of a Ti-Cu (111) single atom alloy: Structure and CO binding. J. Chem. Phys. 2021, 154, 234703.
DOI Google Scholar
48

Patel, D. A.; Hannagan, R. T.; Kress, P. L.; Schilling, A. C.; Çınar, V.; Sykes, E. C. H. Atomic-scale surface structure and CO tolerance of NiCu single-atom alloys. J. Phys. Chem. C 2019, 123, 28142–28147.
DOI Google Scholar
49

Long, R.; Li, Y.; Liu, Y.; Chen, S. M.; Zheng, X. S.; Gao, C.; He, C. H.; Chen, N. S.; Qi, Z. M.; Song, L. et al. Isolation of Cu atoms in Pd lattice: Forming highly selective sites for photocatalytic conversion of CO2 to CH4. J. Am. Chem. Soc. 2017, 139, 4486–4492.
DOI Google Scholar
50

Zhong, Y.; Wang, S. N.; Li, M.; Ma, J.; Song, S. C.; Kumar, A.; Duan, H. H.; Kuang, Y.; Sun, X. M. Rational design of copper-based electrocatalysts and electrochemical systems for CO2 reduction: From active sites engineering to mass transfer dynamics. Mater. Today Phys. 2021, 18, 100354.
DOI Google Scholar
51

Vasileff, A.; Xu, C. 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.
DOI Google Scholar
52

Cheng, T.; Xiao, H.; Goddard, W. A. Reaction mechanisms for the electrochemical reduction of CO2 to CO and formate on the Cu (100) surface at 298 K from quantum mechanics free energy calculations with explicit water. J. Am. Chem. Soc. 2016, 138, 13802–13805.
DOI Google Scholar
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Publication history
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Acknowledgements

Publication history

Received: 23 February 2022
Revised: 25 April 2022
Accepted: 26 April 2022
Published: 02 June 2022
Issue date: August 2022

Copyright

© Tsinghua University Press 2022

Acknowledgements

Acknowledgements

This work is financially supported by the National Natural Science Foundation of China (Nos. 92061109 and 22022504), Natural Science Basic Research Program of Shaanxi (Nos. 2021JCW-20 and S2020-JC-WT-0001), Guangdong “Pearl River” Talent Plan (No. 2019QN01L353), Higher Education Innovation Strong School Project of Guangdong Province of China (No. 2020KTSCX122), Open Project Program of Fujian Key Laboratory of Functional Marine Sensing Materials (No. MJUKF-FMSM202002), and Guangdong Provincial Key Laboratory of Catalysis (No. 2020B121201002). The computational resource is supported from the Center for Computational Science and Engineering at SUSTech and the CHEM high-performance computing cluster (CHEM-HPC) located at the Department of Chemistry, SUSTech.

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