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Nano Research 2023, 16(4): 4698-4705 https://doi.org/10.1007/s12274-022-5134-4
Research Article | Issue | Published: 29 December 2022

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

Show Author's Information 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.

Keywords:
heterostructures, in-situ Raman, CO2 electroreduction, C–C coupling, manipulation of oxidation states
Topics:
Catalysis
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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Abstract Full text Electronic supplementary material About this article

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.


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Electronic supplementary material
About this article

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

Show Author's information 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.

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: heterostructures, in-situ Raman, CO2 electroreduction, C–C coupling, manipulation of oxidation states

References(52)

[1]

Wang, Y. H.; Liu, J. L.; Zheng, G. F. Designing copper-based catalysts for efficient carbon dioxide electroreduction. Adv. Mater. 2021, 33, 2005798.
DOI 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.
DOI 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.
DOI 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.
DOI 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.
DOI 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.
DOI 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.
DOI 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.
DOI 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.
DOI 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.
DOI 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.
DOI 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.
DOI 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.
DOI 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.
DOI 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.
DOI 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.
DOI 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.
DOI 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.
DOI 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.
DOI 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.
DOI 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.
DOI 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.
DOI 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.
DOI 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.
DOI 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.
DOI 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.
DOI 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.
DOI 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.
DOI 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.
DOI 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.
DOI 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.
DOI 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.
DOI 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.
DOI 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.
DOI 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.
DOI 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.
DOI 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.
DOI 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.
DOI Google Scholar
[39]

Pauly, N.; Tougaard, S.; Yubero, F. LMM Auger primary excitation spectra of copper. Surf. Sci. 2014, 630, 294–299.
DOI 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.
DOI 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.
DOI 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.
DOI 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.
DOI 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.
DOI 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.
DOI 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.
DOI 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.
DOI 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.
DOI 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.
DOI 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.
DOI 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.
DOI Google Scholar
[52]

Blyholder, G. Molecular orbital view of chemisorbed carbon monoxide. J. Phys. Chem. 1964, 68, 2772–2777.
DOI Google Scholar
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Publication history
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Acknowledgements

Publication history

Received: 20 September 2022
Revised: 29 September 2022
Accepted: 01 October 2022
Published: 29 December 2022
Issue date: April 2023

Copyright

© Tsinghua University Press 2022

Acknowledgements

Acknowledgements

This work was supported by the National Key R&D Program of China (Nos. 2017YFA0700104 and 2018YFA0702001), the National Natural Science Foundation of China (Nos. 21871238 and 22175163), the Fundamental Research Funds for the Central Universities (No. WK2060000016), and the Youth Innovation Promotion Association of the Chinese Academy of Science (No. 2018494). We thank the photoemission end stations (BL10B) in National Synchrotron Radiation Laboratory (NSRL) and BL14W1 in Shanghai Synchrotron Radiation Facility (SSRF) for help in characterizations.

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