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Research Article

Cu2+1O/CuOx heterostructures promote the electrosynthesis of C2+ products from CO2

Rongbo Sun1,§, Cong Wei1,§, Zixiang Huang3,§, Shuwen Niu1, Xiao Han1, Cai Chen1, Haoran Wang1, Jia Song1, Jun-Dong Yi1, Geng Wu1, Dewei Rao2( ), Xusheng Zheng3, Yuen Wu1, Gongming Wang1( ), Xun Hong1( )
Center of Advanced Nanocatalysis (CAN), Department of Applied Chemistry, University of Science and Technology of China, Hefei 230026, China
School of Materials Science and Engineering, Jiangsu University, Zhenjiang 212013, China
National Synchrotron Radiation Laboratory (NSRL), University of Science and Technology of China, Hefei 230026, China

§ Rongbo Sun, Cong Wei, and Zixiang Huang contributed equally to this work.

Show Author Information

Graphical Abstract

The stable and atypical oxygen-containing copper heterostructures (Cu2+1O/CuOx) are synthesized by a defect construction approach. The adjacent Cu0 and Cuδ+ sites in heterostructured Cu catalyst can efficiently reduce the energy barrier of CO coupling for C2+ products.

Abstract

Manipulating the oxidation state of Cu catalysts can significantly affect the selectivity and activity of electrocatalytic carbon dioxide reduction (CO2RR). However, the thermodynamically favorable cathodic reduction to metallic states typically leads to catalytic deactivation. Herein, a defect construction strategy is employed to prepare crystalline/amorphous Cu2+1O/CuOx heterostructures (c/a-CuOx) with abundant Cu0 and Cuδ+ (0 < δ < 1) sites for CO2RR. The C2+ Faradaic efficiency of the heterostructured Cu catalyst is up to 81.3%, with partial current densities of 406.7 mA·cm−2. Significantly, real-time monitoring of the Cu oxidation state evolution by in-situ Raman spectroscopy confirms the stability of Cuδ+ species under long-term high current density operation. Density functional theory (DFT) calculations further reveal that the adjacent Cu0 and Cuδ+ sites in heterostructured c/a-CuOx can efficiently reduce the energy barrier of CO coupling for C2+ products.

Keywords

CO2 electroreductionC–C couplingheterostructuresin-situ Ramanmanipulation of oxidation states

Electronic Supplementary Material

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References

[1]

Wang, Y. H.; Liu, J. L.; Zheng, G. F. Designing copper-based catalysts for efficient carbon dioxide electroreduction. Adv. Mater. 2021, 33, 2005798.
Crossref Google Scholar
[2]

Wang, J. J.; Zheng, X. R.; Wang, G. J.; Cao, Y. H.; Ding, W. L.; Zhang, J. F.; Wu, H.; Ding, J.; Hu, H. L.; Han, X. P. et al. Defective bimetallic selenides for selective CO2 electroreduction to CO. Adv. Mater. 2022, 34, 2106354.
Crossref Google Scholar
[3]

Sun, X. H.; Tuo, Y. X.; Ye, C. L.; Chen, C.; Lu, Q.; Li, G. N.; Jiang, P.; Chen, S. H.; Zhu, P.; Ma, M. et al. Phosphorus induced electron localization of single iron sites for boosted CO2 electroreduction reaction. Angew. Chem., Int. Ed. 2021, 60, 23614–23618.
Crossref Google Scholar
[4]

Gu, J.; Hsu, C. S.; Bai, L. C.; Chen, H. M.; Hu, X. L. Atomically dispersed Fe3+ sites catalyze efficient CO2 electroreduction to CO. Science 2019, 364, 1091–1094.
Crossref Google Scholar
[5]

Zhang, N. Q.; Zhang, X. X.; Kang, Y. K.; Ye, C. L.; Jin, R.; Yan, H.; Lin, R.; Yang, J. R.; Xu, Q.; Wang, Y. et al. A supported Pd2 dual-atom site catalyst for efficient electrochemical CO2 reduction. Angew. Chem., Int. Ed. 2021, 60, 13388–13393.
Crossref Google Scholar
[6]

Zhang, N. Q.; Zhang, X. X.; Tao, L.; Jiang, P.; Ye, C. L.; Lin, R.; Huang, Z. W.; Li, A.; Pang, D. W.; Yan, H. et al. Silver single-atom catalyst for efficient electrochemical CO2 reduction synthesized from thermal transformation and surface reconstruction. Angew. Chem., Int. Ed. 2021, 60, 6170–6176.
Crossref Google Scholar
[7]

Hepburn, C.; Adlen, E.; Beddington, J.; Carter, E. A.; Fuss, S.; Dowell, N. M.; Minx, J. C.; Smith, P.; Williams, C. K. The technological and economic prospects for CO2 utilization and removal. Nature 2019, 575, 87–97.
Crossref Google Scholar
[8]

Rodrigues, R. M.; Guan, X.; Iñiguez, J. A.; Estabrook, D. A.; Chapman, J. O.; Huang, S. Y.; Sletten, E. M.; Liu, C. Perfluorocarbon nanoemulsion promotes the delivery of reducing equivalents for electricity-driven microbial CO2 reduction. Nat. Catal. 2019, 2, 407–414.
Crossref Google Scholar
[9]

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, 61, e202114450.
Crossref Google Scholar
[10]

De Arquer, F. P. G.; Dinh, C. T.; Ozden, A.; Wicks, J.; McCallum, C.; Kirmani, A. R.; Nam, D. H.; Gabardo, C.; Seifitokaldani, A.; Wang, X. et al. CO2 electrolysis to multicarbon products at activities greater than 1 A·cm−2. Science 2020, 367, 661–666.
Crossref Google Scholar
[11]

Wang, G.; Chen, Z.; Wang, T.; Wang, D. S.; Mao, J. J. P and Cu dual sites on graphitic carbon nitride for photocatalytic CO2 reduction to hydrocarbon fuels with high C2H6 evolution. Angew. Chem., Int. Ed. 2022, 61, e202210789.
Crossref Google Scholar
[12]

Jouny, M.; Hutchings, G. S.; Jiao, F. Carbon monoxide electroreduction as an emerging platform for carbon utilization. Nat. Catal. 2019, 2, 1062–1070.
Crossref Google Scholar
[13]

Zhong, M.; Tran, K.; Min, Y. M.; Wang, C. H.; Wang, Z. Y.; Dinh, C. T.; de Luna, P.; Yu, Z. Q.; Rasouli, A. S.; Brodersen, P. et al. Accelerated discovery of CO2 electrocatalysts using active machine learning. Nature 2020, 581, 178–183.
Crossref Google Scholar
[14]

Li, Y.; Shan, W. T.; Zachman, M. J.; Wang, M. Y.; Hwang, S.; Tabassum, H.; Yang, J.; Yang, X. X.; Karakalos, S.; Feng, Z. X. et al. Atomically dispersed dual-metal site catalysts for enhanced CO2 reduction: Mechanistic insight into active site structures. Angew. Chem., Int. Ed. 2022, 61, e202205632.
Crossref Google Scholar
[15]

Wang, M. M.; Li, M.; Liu, Y. Q.; Zhang, C.; Pan, Y. Structural regulation of single-atomic site catalysts for enhanced electrocatalytic CO2 reduction. Nano Res. 2022, 15, 4925–4941.
Crossref Google Scholar
[16]

Li, R. Z.; Wang, D. S. Understanding the structure-performance relationship of active sites at atomic scale. Nano Res. 2022, 15, 6888–6923.
Crossref Google Scholar
[17]

Tomboc, G. M.; Choi, S.; Kwon, T.; Hwang, Y. J.; Lee, K. Potential link between Cu surface and selective CO2 electroreduction: Perspective on future electrocatalyst designs. Adv. Mater. 2020, 32, 1908398.
Crossref Google Scholar
[18]

Kim, J. Y.; Kim, G.; Won, H.; Gereige, I.; Jung, W. B.; Jung, H. T. Synergistic effect of Cu2O mesh pattern on high-facet Cu surface for selective CO2 electroreduction to ethanol. Adv. Mater. 2022, 34, 2106028.
Crossref Google Scholar
[19]

Arán-Ais, R. M.; Scholten, F.; Kunze, S.; Rizo, R.; Roldan Cuenya, B. The role of in-situ generated morphological motifs and Cu(I) species in C2+ product selectivity during CO2 pulsed electroreduction. Nat. Energy 2020, 5, 317–325.
Crossref Google Scholar
[20]

Zhu, Q. G.; Sun, X. F.; Yang, D. X.; Ma, J.; Kang, X. C.; Zheng, L. R.; Zhang, J.; Wu, Z. H.; Han, B. X. Carbon dioxide electroreduction to C2 products over copper-cuprous oxide derived from electrosynthesized copper complex. Nat. Commun. 2019, 10, 3851.
Crossref Google Scholar
[21]

De Luna, P.; Quintero-Bermudez, R.; Dinh, C. T.; Ross, M. B.; Bushuyev, O. S.; Todorović, P.; Regier, T.; Kelley, S. O.; Yang, P. D.; Sargent, E. H. Catalyst electro-redeposition controls morphology and oxidation state for selective carbon dioxide reduction. Nat. Catal. 2018, 1, 103–110.
Crossref Google Scholar
[22]

Wang, J. L.; Tan, H. Y.; Zhu, Y. P.; Chu, H.; Chen, H. M. Linking the dynamic chemical state of catalysts with the product profile of electrocatalytic CO2 reduction. Angew. Chem., Int. Ed. 2021, 60, 17254–17267.
Crossref Google Scholar
[23]

Wakerley, D.; Lamaison, S.; Ozanam, F.; Menguy, N.; Mercier, D.; Marcus, P.; Fontecave, M.; Mougel, V. Bio-inspired hydrophobicity promotes CO2 reduction on a Cu surface. Nat. Mater. 2019, 18, 1222–1227.
Crossref Google Scholar
[24]

Wu, Z. Z.; Gao, F. Y.; Gao, M. R. Regulating the oxidation state of nanomaterials for electrocatalytic CO2 reduction. Energy Environ. Sci. 2021, 14, 1121–1139.
Crossref Google Scholar
[25]

Liu, J. Z.; Cheng, L.; Wang, Y. T.; Chen, R. Z.; Xiao, C. Q.; Zhou, X. D.; Zhu, Y. H.; Li, Y. H.; Li, C. Z. Dynamic determination of Cu+ roles for CO2 reduction on electrochemically stable Cu2O-based nanocubes. J. Mater. Chem. A 2022, 10, 8459–8465.
Crossref Google Scholar
[26]

Yang, P. P.; Zhang, X. L.; Gao, F. Y.; Zheng, Y. R.; Niu, Z. Z.; Yu, X. X.; Liu, R.; Wu, Z. Z.; Qin, S.; Chi, L. P. et al. Protecting copper oxidation state via intermediate confinement for selective CO2 electroreduction to C2+ fuels. J. Am. Chem. Soc. 2020, 142, 6400–6408.
Crossref Google Scholar
[27]

Zang, Y. P.; Liu, T. F.; Wei, P. F.; Li, H. F.; Wang, Q.; Wang, G. X.; Bao, X. H. Selective CO2 electroreduction to ethanol over a carbon-coated CuOx catalyst. Angew. Chem., Int. Ed. 2022, 61, e202209629.
Crossref Google Scholar
[28]

Martić, N.; Reller, C.; Macauley, C.; Löffler, M.; Schmid, B.; Reinisch, D.; Volkova, E.; Maltenberger, A.; Rucki, A.; Mayrhofer, K. J. J. et al. Paramelaconite-enriched copper-based material as an efficient and robust catalyst for electrochemical carbon dioxide reduction. Adv. Energy Mater. 2019, 9, 1901228.
Crossref Google Scholar
[29]

Wang, R.; Liu, J.; Huang, Q.; Dong, L. Z.; Li, S. L.; Lan, Y. Q. Partial coordination-perturbed Bi-copper sites for selective electroreduction of CO2 to hydrocarbons. Angew. Chem., Int. Ed. 2021, 60, 19829–19835.
Crossref Google Scholar
[30]

Li, F. W.; Thevenon, A.; Rosas-Hernández, A.; Wang, Z. Y.; Li, Y. L.; Gabardo, C. M.; Ozden, A.; Dinh, C. T.; Li, J.; Wang, Y. H. et al. Molecular tuning of CO2-to-ethylene conversion. Nature 2020, 577, 509–513.
Crossref Google Scholar
[31]

Duan, G. Y.; Li, X. Q.; Ding, G. R.; Han, L. J.; Xu, B. H.; Zhang, S. J. Highly efficient electrocatalytic CO2 reduction to C2+ products on a poly(ionic liquid)-based Cu0-CuI tandem catalyst. Angew. Chem., Int. Ed. 2022, 61, e202110657.
Crossref Google Scholar
[32]

Li, H. F.; Liu, T. F.; Wei, P. F.; Lin, L.; Gao, D. F.; Wang, G. X.; Bao, X. H. High-rate CO2 electroreduction to C2+ products over a copper-copper iodide catalyst. Angew. Chem., Int. Ed. 2021, 60, 14329–14333.
Crossref Google Scholar
[33]

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.
Crossref Google Scholar
[34]

Chen, C. B.; Li, Y. F.; Yu, S.; Louisia, S.; Jin, J. B.; Li, M. F.; Ross, M. B.; Yang, P. D. Cu-Ag tandem catalysts for high-rate CO2 electrolysis toward multicarbons. Joule 2020, 4, 1688–1699.
Crossref Google Scholar
[35]

Sun, R. B.; Gao, J. Y.; Wu, G.; Liu, P. G.; Guo, W. X.; Zhou, H.; Ge, J. J.; Hu, Y. M.; Xue, Z. G.; Li, H. et al. Amorphous metal oxide nanosheets featuring reversible structure transformations as sodium-ion battery anodes. Cell Rep. Phys. Sci. 2020, 1, 100118.
Crossref Google Scholar
[36]

Chu, Y. T.; Guo, L. Y.; Xi, B. J.; Feng, Z. Y.; Wu, F. F.; Lin, Y.; Liu, J. C.; Sun, D.; Feng, J. K.; Qian, Y. T. et al. Embedding MnO@Mn3O4 nanoparticles in an N-doped-carbon framework derived from Mn-organic clusters for efficient lithium storage. Adv. Mat. 2018, 30, 1704244.
Crossref Google Scholar
[37]

Chen, K. F.; Lo, S. C.; Chang, L.; Egerton, R.; Kai, J. J.; Lin, J. J.; Chen, F. R. Valence state map of iron oxide thin film obtained from electron spectroscopy imaging series. Micron 2007, 38, 354–361.
Crossref Google Scholar
[38]

Tahir, D.; Tougaard, S. Electronic and optical properties of Cu, CuO, and Cu2O studied by electron spectroscopy. J. Phys. Condens. Matter 2012, 24, 175002.
Crossref Google Scholar
[39]

Pauly, N.; Tougaard, S.; Yubero, F. LMM Auger primary excitation spectra of copper. Surf. Sci. 2014, 630, 294–299.
Crossref Google Scholar
[40]

Tian, Y. H.; Liu, X. Z.; Xu, L.; Yuan, D.; Dou, Y. H.; Qiu, J. X.; Li, H. N.; Ma, J. M.; Wang, Y.; Su, D. et al. Engineering crystallinity and oxygen vacancies of Co(II) oxide nanosheets for high performance and robust rechargeable Zn-air batteries. Adv. Funct. Mater. 2021, 31, 2101239.
Crossref Google Scholar
[41]

Velasco-Vélez, J. J.; Jones, T.; Gao, D. F.; Carbonio, E.; Arrigo, R.; Hsu, C. J.; Huang, Y. C.; Dong, C. L.; Chen, J. M.; Lee, J. F. et al. The role of the copper oxidation state in the electrocatalytic reduction of CO2 into valuable hydrocarbons. ACS Sustainable Chem. Eng. 2019, 7, 1485–1492.
Crossref Google Scholar
[42]

Wu, G.; Zheng, X. S.; Cui, P. X.; Jiang, H. Y.; Wang, X. Q.; Qu, Y. T.; Chen, W. X.; Lin, Y.; Li, H.; Han, X. et al. A general synthesis approach for amorphous noble metal nanosheets. Nat. Commun. 2019, 10, 4855.
Crossref Google Scholar
[43]

Gao, J.; Zhang, H.; Guo, X. Y.; Luo, J. S.; Zakeeruddin, S. M.; Ren, D.; Grätzel, M. Selective C–C coupling in carbon dioxide electroreduction via efficient spillover of intermediates as supported by operando Raman spectroscopy. J. Am. Chem. Soc. 2019, 141, 18704–18714.
Crossref Google Scholar
[44]

Chernyshova, I. V.; Somasundaran, P.; Ponnurangam, S. On the origin of the elusive first intermediate of CO2 electroreduction. Proc. Natl. Acad. Sci. USA 2018, 115, E9261–E9270.
Crossref Google Scholar
[45]

Jiang, Y. W.; Wang, X. Y.; Duan, D. L.; He, C. H.; Ma, J.; Zhang, W. Q.; Liu, H. J.; Long, R.; Li, Z. B.; Kong, T. T. et al. Structural reconstruction of Cu2O superparticles toward electrocatalytic CO2 reduction with high C2+ products selectivity. Adv. Sci. 2022, 9, 2105292.
Crossref Google Scholar
[46]

Ross, M. B.; Dinh, C. T.; Li, Y. F.; Kim, D.; de Luna, P.; Sargent, E. H.; Yang, P. D. Tunable Cu enrichment enables designer syngas electrosynthesis from CO2. J. Am. Chem. Soc. 2017, 139, 9359–9363.
Crossref Google Scholar
[47]

Kim, Y.; Park, S.; Shin, S. J.; Choi, W.; Min, B. K.; Kim, H.; Kim, W.; Hwang, Y. J. Time-resolved observation of C–C coupling intermediates on Cu electrodes for selective electrochemical CO2 reduction. Energy Environ. Sci. 2020, 13, 4301–4311.
Crossref Google Scholar
[48]

Mudiyanselage, K.; Kim, H. Y.; Senanayake, S. D.; Baber, A. E.; Liu, P.; Stacchiola, D. Probing adsorption sites for CO on ceria. Phys. Chem. Chem. Phys. 2013, 15, 15856–15862.
Crossref Google Scholar
[49]

Nitopi, S.; Bertheussen, E.; Scott, S. B.; Liu, X. Y.; Engstfeld, A. K.; Horch, S.; Seger, B.; Stephens, I. E. L.; Chan, K.; Hahn, C. et al. Progress and perspectives of electrochemical CO2 reduction on copper in aqueous electrolyte. Chem. Rev. 2019, 119, 7610–7672.
Crossref Google Scholar
[50]

Liu, X. Y.; Xiao, J. P.; Peng, H. J.; Hong, X.; Chan, K. R.; Nørskov, J. K. Understanding trends in electrochemical carbon dioxide reduction rates. Nat. Commun. 2017, 8, 15438.
Crossref Google Scholar
[51]

Chan, K. R.; Tsai, C.; Hansen, H. A.; Nørskov, J. K. Molybdenum sulfides and selenides as possible electrocatalysts for CO2 reduction. ChemCatChem 2014, 6, 1899–1905.
Crossref Google Scholar
[52]

Blyholder, G. Molecular orbital view of chemisorbed carbon monoxide. J. Phys. Chem. 1964, 68, 2772–2777.
Crossref Google Scholar
Nano Research
Volume 16 Issue 4,
April 2023
Pages 4698-4705
DOI: 10.1007/s12274-022-5134-4
Cite this article:
Sun R, Wei C, Huang Z, et al. Cu2+1O/CuOx heterostructures promote the electrosynthesis of C2+ products from CO2. Nano Research, 2023, 16(4): 4698-4705. https://doi.org/10.1007/s12274-022-5134-4
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Received: 20 September 2022
Revised: 29 September 2022
Accepted: 01 October 2022
Published: 29 December 2022
© Tsinghua University Press 2022
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