Complementary Operando Spectroscopy identification of in-situ generated metastable charge-asymmetry Cu2-CuN3 clusters for CO2 reduction to ethanol

Xiaozhi Su; Zhuoli Jiang; Jing Zhou; Hengjie Liu; Danni Zhou; Huishan Shang; Xingming Ni; Zheng Peng; Fan Yang; Wenxing Chen; Zeming Qi; Dingsheng Wang; Yu Wang

doi:10.1038/s41467-022-29035-8

Complementary Operando Spectroscopy identification of in-situ generated metastable charge-asymmetry Cu₂-CuN₃ clusters for CO₂ reduction to ethanol

Nat Commun. 2022 Mar 11;13(1):1322. doi: 10.1038/s41467-022-29035-8.

Authors

Xiaozhi Su^#¹, Zhuoli Jiang^#^{2

3}, Jing Zhou^#⁴, Hengjie Liu⁵, Danni Zhou², Huishan Shang², Xingming Ni⁶, Zheng Peng⁶, Fan Yang⁶, Wenxing Chen⁷, Zeming Qi⁵, Dingsheng Wang³, Yu Wang⁸

Affiliations

¹ Shanghai Synchrotron Radiation Facility, Zhangjiang Laboratory, Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai, 201204, China.
² Beijing Key Laboratory of Construction Tailorable Advanced Functional Materials and Green Applications, School of Materials Science and Engineering, Beijing Institute of Technology, Beijing, 100081, China.
³ Department of Chemistry, Tsinghua University, Beijing, 100084, China.
⁴ Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai, 201800, China.
⁵ National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei, Anhui, 230029, China.
⁶ School of Physical Science and Technology, ShanghaiTech University, Shanghai, 201210, China.
⁷ Beijing Key Laboratory of Construction Tailorable Advanced Functional Materials and Green Applications, School of Materials Science and Engineering, Beijing Institute of Technology, Beijing, 100081, China. wxchen@bit.edu.cn.
⁸ Shanghai Synchrotron Radiation Facility, Zhangjiang Laboratory, Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai, 201204, China. wangyu@sinap.ac.cn.

^# Contributed equally.

Abstract

Copper-based materials can reliably convert carbon dioxide into multi-carbon products but they suffer from poor activity and product selectivity. The atomic structure-activity relationship of electrocatalysts for the selectivity is controversial due to the lacking of systemic multiple dimensions for operando condition study. Herein, we synthesized high-performance CO₂RR catalyst comprising of CuO clusters supported on N-doped carbon nanosheets, which exhibited high C₂₊ products Faradaic efficiency of 73% including decent ethanol selectivity of 51% with a partial current density of 14.4 mA/cm^-2 at -1.1 V vs. RHE. We evidenced catalyst restructuring and tracked the variation of the active states under reaction conditions, presenting the atomic structure-activity relationship of this catalyst. Operando XAS, XANES simulations and Quasi-in-situ XPS analyses identified a reversible potential-dependent transformation from dispersed CuO clusters to Cu₂-CuN₃ clusters which are the optimal sites. This cluster can't exist without the applied potential. The N-doping dispersed the reduced Cu_n clusters uniformly and maintained excellent stability and high activity with adjusting the charge distribution between the Cu atoms and N-doped carbon interface. By combining Operando FTIR and DFT calculations, it was recognized that the Cu₂-CuN₃ clusters displayed charge-asymmetric sites which were intensified by CH₃^* adsorbing, beneficial to the formation of the high-efficiency asymmetric ethanol.

Abstract

Grants and funding