Grain Boundary‐Derived Cu + /Cu 0 Interfaces in CuO Nanosheets for Low Overpotential Carbon Dioxide Electroreduction to Ethylene

Zhang, Jianfang; Wang, Yan; Li, Zhengyuan; Xia, Shuai; Cai, Rui; Ma, Lu; Zhang, Tianyu; Ackley, Josh; Yang, Shize; Wu, Yucheng; Wu, Jingjie

doi:10.1002/advs.202200454

Title: Grain Boundary‐Derived Cu ⁺ /Cu ⁰ Interfaces in CuO Nanosheets for Low Overpotential Carbon Dioxide Electroreduction to Ethylene

Journal Article · 21 May 2022 · Advanced Science

DOI: https://doi.org/10.1002/advs.202200454 · OSTI ID:1869354

^[1]; Wang, Yan ^[2]; Li, Zhengyuan ^[3]; Xia, Shuai ^[2]; Cai, Rui ^[2]; Ma, Lu ^[4]; Zhang, Tianyu ^[3]; Ackley, Josh ^[3]; Yang, Shize ^[5]; Wu, Yucheng ^[6];

^[3]

School of Materials Science and Engineering Hefei University of Technology Hefei 230009 China, Department of Chemical and Environmental Engineering University of Cincinnati Cincinnati OH 45221 USA
School of Materials Science and Engineering Hefei University of Technology Hefei 230009 China
Department of Chemical and Environmental Engineering University of Cincinnati Cincinnati OH 45221 USA
National Synchrotron Light Source II Brookhaven National Laboratory Upton NY 11971 USA
Eyring Materials Center Arizona State University 85287 Tempe AZ USA
School of Materials Science and Engineering Hefei University of Technology Hefei 230009 China, China International S&,T Cooperation Base for Advanced Energy and Environmental Materials and Anhui Provincial International S&,T Cooperation Base for Advanced Energy Materials Hefei University of Technology Hefei 230009 China

Abstract Electrochemical CO ₂ reduction reaction can be used to produce value‐added hydrocarbon fuels and chemicals by coupling with clean electrical energy. However, highly active, selective, and energy‐efficient CO ₂ conversion to multicarbon hydrocarbons, such as C ₂ H ₄ , remains challenging because of the lack of efficient catalysts. Herein, an ultrasonication‐assisted electrodeposition strategy to synthesize CuO nanosheets for low‐overpotential CO ₂ electroreduction to C ₂ H ₄ is reported. A high C ₂ H ₄ Faradaic efficiency of 62.5% is achieved over the CuO nanosheets at a small potential of −0.52 V versus a reversible hydrogen electrode, corresponding to a record high half‐cell cathodic energy efficiency of 41%. The selectivity toward C ₂ H ₄ is maintained for over 60 h of continuous operation. The CuO nanosheets are prone to in situ restructuring during CO ₂ reduction, forming abundant grain boundaries (GBs). Stable Cu ⁺ /Cu ⁰ interfaces are derived from the low‐coordinated Cu atoms in the reconstructed GB regions and act as highly active sites for CO ₂ reduction at low overpotentials. In situ Raman spectroscopic analysis and density functional theory computation reveal that the Cu ⁺ /Cu ⁰ interfaces offer high *CO surface coverage and lower the activation energy barrier for *CO dimerization, which, in synergy, facilitates CO ₂ reduction to C ₂ H ₄ at low overpotentials.

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Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: China Postdoctoral Science Foundation; Key R&D Projects of Anhui Province; National Natural Science Foundation of China (NSFC); USDOE; USDOE Office of Energy Efficiency and Renewable Energy (EERE); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: EE0009421; SC0012704

OSTI ID:: 1869354

Report Number(s):: BNL-223521-2022-JAAM; 2200454

Journal Information:: Advanced Science, Journal Name: Advanced Science Journal Issue: 21 Vol. 9; ISSN 2198-3844

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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36 MATERIALS SCIENCE
CO2 reduction
Cu+/Cu0 interfaces
ethylene
grain boundary
low overpotential

Title: Grain Boundary‐Derived Cu + /Cu 0 Interfaces in CuO Nanosheets for Low Overpotential Carbon Dioxide Electroreduction to Ethylene

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Title: Grain Boundary‐Derived Cu ⁺ /Cu ⁰ Interfaces in CuO Nanosheets for Low Overpotential Carbon Dioxide Electroreduction to Ethylene