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Research Article

Selectivity regulation of CO2 electroreduction through contact interface engineering on superwetting Cu nanoarray electrodes

Zhao Cai1,§, Yusheng Zhang1,§, Yuxin Zhao4,§, Yueshen Wu2, Wenwen Xu1,2, Xuemei Wen1, Yang Zhong1,3, Ying Zhang5( ), Wen Liu1, Hailiang Wang2, Yun Kuang1( ), Xiaoming Sun1,3( )
State Key Laboratory of Chemical Resource Engineering,Beijing Advanced Innovation Center for Soft Matter Science and Engineering, Beijing University of Chemical Technology,Beijing,100029,China;
Department of Chemistry and Energy Sciences Institute,Yale University,West Haven, Connecticut,06516,USA;
College of Energy,Beijing University of Chemical Technology,Beijing,100029,China;
State Key Laboratory of Safety and Control for Chemicals,SINOPEC Research Institute of Safety Engineering, No.339, Songling road, Laoshan District,Qingdao,266101,China;
School of Chemistry,Monash University,Wellington Road, Clayton,3800,VIC, Australia;

§ Zhao Cai, Yusheng Zhang, and Yuxin Zhao contributed equally to this work.

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Graphical Abstract

Abstract

Electrocatalytic CO2 reduction is a promising way to mitigate the urgent energy and environmental issues, but how to increase the selectivity for desired product among multiple competing reaction pathways remains a bottleneck. Here, we demonstrate that engineering the gas–liquid–solid contact interface on the electrode surface could tailor the selectivity of CO2 reduction and meanwhile suppress H2 production through regulated reaction kinetics. Specifically, polytetrafluoroethylene (PTFE) was utilized to modify a Cu nanoarray electrode as an example, which is able to change the electrode surface from aerophobic to aerophilic state. The enriched nano-tunnels of the Cu nanoarray electrode can facilitate CO2 transportation and pin gaseous products on the electrode surface. The latter is believed to be the reason that boosts the Faradaic efficiency of liquid products by 67% and limits the H2 production to less than half of before. This interface engineering strategy also lowered H2O (proton) affinity, therefore promoting CO and HCOOH production. Engineering the electrode contact interface controls the reaction kinetics and the selectivity of products, which should be inspiring for other electrochemical reactions.

Keywords

CO2 reductionselectivitycoppercontact interfacereaction kinetics

Electronic Supplementary Material

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References

1

Schreier, M.; Héroguel, F.; Steier, L.; Ahmad, S.; Luterbacher, J. S.; Mayer, M. T.; Luo, J. S.; Grätzel, M. Solar conversion of CO2 to CO using earthabundant electrocatalysts prepared by atomic layer modification of CuO. Nat. Energy 2017, 2, 17087.
Crossref Google Scholar
2

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.
Crossref Google Scholar
3

Qiao, J. L.; Liu, Y. Y.; Hong, F.; Zhang, J. J. A review of catalysts for the electroreduction of carbon dioxide to produce low-carbon fuels. Chem. Soc. Rev. 2014, 43, 631-675.
Crossref Google Scholar
4

Lei, F. C.; Liu, W.; Sun, Y. F.; Xu, J. Q.; Liu, K. T.; Liang, L.; Yao, T.; Pan, B. C.; Wei, S. Q.; Xie, Y. Metallic tin quantum sheets confined in graphene toward high-efficiency carbon dioxide electroreduction. Nat. Commun. 2016, 7, 12697.
Crossref Google Scholar
5

Gao, S.; Sun, Z. T.; Liu, W.; Jiao, X. C.; Zu, X. L.; Hu, Q. T.; Sun, Y. F.; Yao, T.; Zhang, W. H.; Wei, S. Q. et al. Atomic layer confined vacancies for atomic-level insights into carbon dioxide electroreduction. Nat. Commun. 2017, 8, 14503.
Crossref Google Scholar
6

Chen, Y. H.; Kanan, M. W. Tin oxide dependence of the CO2 reduction efficiency on tin electrodes and enhanced activity for tin/tin oxide thin-film catalysts. J. Am. Chem. Soc. 2012, 134, 1986-1989.
Crossref Google Scholar
7

Li, F. W.; Chen, L.; Knowles, G. P.; MacFarlane, D. R.; Zhang, J. Hierarchical mesoporous SnO2 nanosheets on carbon cloth: A robust and flexible electrocatalyst for CO2 reduction with high efficiency and selectivity. Angew. Chem., Int. Ed. 2017, 56, 505-509.
Crossref Google Scholar
8

Jiang, K.; Wang, H.; Cai, W. B.; Wang, H. T. Li electrochemical tuning of metal oxide for highly selective CO2 reduction. ACS Nano 2017, 11, 6451-6458.
Crossref Google Scholar
9

Zhang, S.; Kang, P.; Meyer, T. J. Nanostructured tin catalysts for selective electrochemical reduction of carbon dioxide to formate. J. Am. Chem. Soc. 2014, 136, 1734-1737.
Crossref Google Scholar
10

Kim, C.; Jeon, H. S.; Eom, T.; Jee, M. S.; Kim, H.; Friend, C. M.; Min, B. K.; Hwang, Y. J. Achieving selective and efficient electrocatalytic activity for CO2 reduction using immobilized silver nanoparticles. J. Am. Chem. Soc. 2015, 137, 13844-13850.
Crossref Google Scholar
11

Liu, S. B.; Tao, H. B.; Zeng, L.; Liu, Q.; Xu, Z. H.; Liu, Q. X.; Luo, J. L. Shape-dependent electrocatalytic reduction of CO2 to CO on triangular silver nanoplates. J. Am. Chem. Soc. 2017, 139, 2160-2163.
Crossref Google Scholar
12

Luc, W.; Collins, C.; Wang, S. W.; Xin, H. L.; He, K.; Kang, Y. J.; Jiao, F. Ag-Sn bimetallic catalyst with a core-shell structure for CO2 reduction. J. Am. Chem. Soc. 2017, 139, 1885-1893.
Crossref Google Scholar
13

Gao, D. F.; Zhang, Y.; Zhou, Z. W.; Cai, F.; Zhao, X. F.; Huang, W. G.; Li, Y. S.; Zhu, J. F.; Liu, P.; Yang, F. et al. Enhancing CO2 electroreduction with the metal-oxide interface. J. Am. Chem. Soc. 2017, 139, 5652-5655.
Crossref Google Scholar
14

Kumar, B.; Atla, V.; Brian, J. P.; Kumari, S.; Nguyen, T. Q.; Sunkara, M.; Spurgeon, J. M. Reduced SnO2 porous nanowires with a high density of grain boundaries as catalysts for efficient electrochemical CO2-into-HCOOH conversion. Angew. Chem., Int. Ed. 2017, 56, 3645-3649.
Crossref Google Scholar
15

Huo, S. J.; Weng, Z.; Wu, Z. S.; Zhong, Y. R.; Wu, Y. S.; Fang, J. H.; Wang, H. L. Coupled metal/oxide catalysts with tunable product selectivity for electrocatalytic CO2 reduction. ACS Appl. Mater. Interfaces 2017, 9, 28519-28526.
Crossref Google Scholar
16

Varela, A. S.; Ju, W.; Reier, T.; Strasser, P. Tuning the catalytic activity and selectivity of Cu for CO2 electroreduction in the presence of halides. ACS Catal. 2016, 6, 2136-2144.
Crossref Google Scholar
17

Hahn, C.; Hatsukade, T.; Kim, Y. G.; Vailionis, A.; Baricuatro, J. H.; Higgins, D. C.; Nitopi, S. A.; Soriaga, M. P.; Jaramillo, T. F. Engineering Cu surfaces for the electrocatalytic conversion of CO2: Controlling selectivity toward oxygenates and hydrocarbons. Proc. Natl. Acad. Sci. USA 2017, 114, 5918-5923.
Crossref Google Scholar
18

Weng, Z.; Zhang, X.; Wu, Y. S.; Huo, S. J.; Jiang, J. B.; Liu, W.; He, G. J.; Liang, Y. Y.; Wang, H. L. Self-cleaning catalyst electrodes for stabilized CO2 reduction to hydrocarbons. Angew. Chem., Int. Ed. 2017, 56, 13135-13139.
Crossref Google Scholar
19

Weng, Z.; Jiang, J. B.; Wu, Y. S.; Wu, Z. S.; Guo, X. T.; Materna, K. L.; Liu, W.; Batista, V. S.; Brudvig, G. W.; Wang, H. L. Electrochemical CO2 reduction to hydrocarbons on a heterogeneous molecular Cu catalyst in aqueous solution. J. Am. Chem. Soc. 2016, 138, 8076-8079.
Crossref Google Scholar
20

Li, Q.; Fu, J. J.; Zhu, W. L.; Chen, Z. Z.; Shen, B.; Wu, L. H.; Xi, Z.; Wang, T. Y.; Lu, G.; Zhu, J. J. et al. Tuning Sn-catalysis for electrochemical reduction of CO2 to CO via the core/shell Cu/SnO2 structure. J. Am. Chem. Soc. 2017, 139, 4290-4293.
Crossref Google Scholar
21

Li, Y. F.; Cui, F.; Ross, M. B.; Kim, D.; Sun, Y. C.; Yang, P. D. Structuresensitive CO2 electroreduction to hydrocarbons on ultrathin 5-fold twinned copper nanowires. Nano Lett. 2017, 17, 1312-1317.
Crossref Google Scholar
22

Dai, L.; Qin, Q.; Wang, P.; Zhao, X. J.; Hu, C. Y.; Liu, P. X.; Qin, R. X.; Chen, M.; Ou, D. H.; Xu, C. F. et al. Ultrastable atomic copper nanosheets for selective electrochemical reduction of carbon dioxide. Sci. Adv. 2017, 3, e1701069.
Crossref Google Scholar
23

Ma, S. C.; Sadakiyo, M.; Heima, M.; Luo, R.; Haasch, R. T.; Gold, J. I.; Yamauchi, M.; Kenis, P. J. A. Electroreduction of carbon dioxide to hydrocarbons using bimetallic Cu-Pd catalysts with different mixing patterns. J. Am. Chem. Soc. 2016, 139, 47-50.
Google Scholar
24

Sarfraz, S.; Garcia-Esparza, A. T.; Jedidi, A.; Cavallo, L.; Takanabe, K. Cu-Sn bimetallic catalyst for selective aqueous electroreduction of CO2 to CO. ACS Catal. 2016, 6, 2842-2851.
Crossref Google Scholar
25

Li, C. W.; Kanan, M. W. CO2 reduction at low overpotential on Cu electrodes resulting from the reduction of thick Cu2O films. J. Am. Chem. Soc. 2012, 134, 7231-7234.
Crossref Google Scholar
26

Verdaguer-Casadevall, A.; Li, C. W.; Johansson, T. P.; Scott, S. B.; McKeown, J. T.; Kumar, M.; Stephens, I. E. L.; Kanan, M. W.; Chorkendorff, I. Probing the active surface sites for CO reduction on oxide-derived copper electrocatalysts. J. Am. Chem. Soc. 2015, 137, 9808-9811.
Crossref Google Scholar
27

Li, P. S.; Xie, Q. X.; Zheng, L. R.; Feng, G.; Li, Y. J.; Cai, Z.; Bi, Y. M.; Li, Y. P.; Kuang, Y.; Sun, X. M. et al. Topotactic reduction of layered double hydroxides for atomically thick two-dimensional non-noble-metal alloy. Nano Res. 2017, 10, 2988-2997.
Crossref Google Scholar
28

Weng, Z.; Wu, Y. S.; Wang, M. Y.; Jiang, J. B.; Yang, K.; Huo, S. J.; Wang, X. F.; Ma, Q.; Brudvig, G. W.; Batista, V. S. et al. Active sites of coppercomplex catalytic materials for electrochemical carbon dioxide reduction. Nat. Commun. 2018, 9, 415.
Crossref Google Scholar
29

Cai, Z.; Zhou, D. J.; Wang, M. Y.; Bak, S. M.; Wu, Y. S.; Wu, Z. S.; Tian, Y.; Xiong, X. Y.; Li, Y. P.; Liu, W. et al. Introducing Fe2+ into nickel-iron layered double hydroxide: Local structure modulated water oxidation activity. Angew. Chem., Int. Ed. 2018, 130, 9536-9540.
Crossref Google Scholar
30

Zhou, D. J.; Cai, Z.; Lei, X. D.; Tian, W. L.; Bi, Y. M.; Jia, Y.; Han, N. N.; Gao, T. F.; Zhang, Q.; Kuang, Y. et al. NiCoFe-layered double hydroxides/ N-doped graphene oxide array colloid composite as an efficient bifunctional catalyst for oxygen electrocatalytic reactions. Adv. Energy Mater. 2018, 8, 1701905.
Crossref Google Scholar
31

Han, N. N.; Yang, K. R.; Lu, Z. Y.; Li, Y. J.; Xu, W. W.; Gao, T. F.; Cai, Z.; Zhang, Y.; Batista, V. S.; Liu, W. et al. Nitrogen-doped tungsten carbide nanoarray as an efficient bifunctional electrocatalyst for water splitting in acid. Nat. Commun. 2018, 9, 924.
Crossref Google Scholar
32

Cai, Z.; Bi, Y. M.; Hu, E. Y.; Liu, W.; Dwarica, N.; Tian, Y.; Li, X. L.; Kuang, Y.; Li, Y. P.; Yang, X. Q. et al. Single-crystalline ultrathin Co3O4 nanosheets with massive vacancy defects for enhanced electrocatalysis. Adv. Energy Mater. 2018, 8, 1701694.
Crossref Google Scholar
33

Zhou, Y.; Silva, J. L.; Woods, J. M.; Pondick, J. V.; Feng, Q. L.; Liang, Z. X.; Liu, W.; Lin, L.; Deng, B. C.; Brena, B. et al. Revealing the contribution of individual factors to hydrogen evolution reaction catalytic activity. Adv. Mater. 2018, 30, 1706076.
Crossref Google Scholar
34

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.
Crossref Google Scholar
35

Lu, Z. Y.; Xu, W. W.; Ma, J.; Li, Y. J.; Sun, X. M.; Jiang, L. Superaerophilic carbon-nanotube-array electrode for high-performance oxygen reduction reaction. Adv. Mater. 2016, 28, 7155-7161.
Crossref Google Scholar
36

Lu, Z. Y.; Zhu, W.; Yu, X. Y.; Zhang, H. C.; Li, Y. J.; Sun, X. M.; Wang, X. W.; Wang, H.; Wang, J. M.; Luo, J. et al. Ultrahigh hydrogen evolution performance of under-water "superaerophobic" MoS2 nanostructured electrodes. Adv. Mater. 2014, 26, 2683-2687.
Crossref Google Scholar
37

Tian, X. L.; Verho, T.; Ras, R. H. A. Moving superhydrophobic surfaces toward real-world applications. Science 2016, 352, 142-143.
Crossref Google Scholar
38

Morales-Guio, C. G.; Stern, L. A.; Hu, X. L. Nanostructured hydrotreating catalysts for electrochemical hydrogen evolution. Chem. Soc. Rev. 2014, 43, 6555-6569.
Crossref Google Scholar
39

Zhu, S. Q.; Jiang, B.; Cai, W. B.; Shao, M. H. Direct observation on reaction intermediates and the role of bicarbonate anions in CO2 electrochemical reduction reaction on Cu surfaces. J. Am. Chem. Soc. 2017, 139, 15664-15667.
Crossref Google Scholar
40

Schouten, K. J. P.; Kwon, Y.; Van der Ham, C. J. M.; Qin, Z.; Koper, M. T. M. A new mechanism for the selectivity to C1 and C2 species in the electrochemical reduction of carbon dioxide on copper electrodes. Chem. Sci. 2011, 2, 1902-1909.
Crossref Google Scholar
Nano Research
Volume 12 Issue 2,
February 2019
Pages 345-349
DOI: 10.1007/s12274-018-2221-7
Cite this article:
Cai Z, Zhang Y, Zhao Y, et al. Selectivity regulation of CO2 electroreduction through contact interface engineering on superwetting Cu nanoarray electrodes. Nano Research, 2019, 12(2): 345-349. https://doi.org/10.1007/s12274-018-2221-7
Topics:
Carbon dioxideCatalyst selectivity CopperElectrolytic reduction Hydrogen productionKinetics

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Received: 21 July 2018
Revised: 13 September 2018
Accepted: 10 October 2018
Published: 23 October 2018
© Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature 2018
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