Issue

Vol. 16 (2024)

Atomic Dispersed Hetero-Pairs for Enhanced Electrocatalytic CO2 Reduction

https://doi.org/10.1007/s40820-023-01214-2
Zhaoyong Jin
State Key Laboratory of Automotive Simulation and Control, School of Materials Science and Engineering, Key Laboratory of Automobile Materials of MOE, Electron Microscopy Center, Jilin University, Changchun 130012, People’s Republic of China
Meiqi Yang
Key Laboratory of Photonic and Electronic Bandgap Materials, Ministry of Education, and College of Chemistry and Chemical Engineering, Harbin Normal University, Harbin 150025, People’s Republic of China
Yilong Dong
State Key Laboratory of Automotive Simulation and Control, School of Materials Science and Engineering, Key Laboratory of Automobile Materials of MOE, Electron Microscopy Center, Jilin University, Changchun 130012, People’s Republic of China
Xingcheng Ma
State Key Laboratory of Automotive Simulation and Control, School of Materials Science and Engineering, Key Laboratory of Automobile Materials of MOE, Electron Microscopy Center, Jilin University, Changchun 130012, People’s Republic of China
Ying Wang
State Key Laboratory of Automotive Simulation and Control, School of Materials Science and Engineering, Key Laboratory of Automobile Materials of MOE, Electron Microscopy Center, Jilin University, Changchun 130012, People’s Republic of China
Jiandong Wu
State Key Laboratory of Automotive Simulation and Control, School of Materials Science and Engineering, Key Laboratory of Automobile Materials of MOE, Electron Microscopy Center, Jilin University, Changchun 130012, People’s Republic of China
Jinchang Fan
State Key Laboratory of Automotive Simulation and Control, School of Materials Science and Engineering, Key Laboratory of Automobile Materials of MOE, Electron Microscopy Center, Jilin University, Changchun 130012, People’s Republic of China
Dewen Wang
State Key Laboratory of Automotive Simulation and Control, School of Materials Science and Engineering, Key Laboratory of Automobile Materials of MOE, Electron Microscopy Center, Jilin University, Changchun 130012, People’s Republic of China
Rongshen Xi
State Key Laboratory of Automotive Simulation and Control, School of Materials Science and Engineering, Key Laboratory of Automobile Materials of MOE, Electron Microscopy Center, Jilin University, Changchun 130012, People’s Republic of China
Xiao Zhao
State Key Laboratory of Automotive Simulation and Control, School of Materials Science and Engineering, Key Laboratory of Automobile Materials of MOE, Electron Microscopy Center, Jilin University, Changchun 130012, People’s Republic of China
Tianyi Xu
State Key Laboratory of Automotive Simulation and Control, School of Materials Science and Engineering, Key Laboratory of Automobile Materials of MOE, Electron Microscopy Center, Jilin University, Changchun 130012, People’s Republic of China
Jingxiang Zhao
Key Laboratory of Photonic and Electronic Bandgap Materials, Ministry of Education, and College of Chemistry and Chemical Engineering, Harbin Normal University, Harbin 150025, People’s Republic of China
Lei Zhang
College of Chemistry, Jilin University, Changchun 130012, People’s Republic of China
David J. Singh
Department of Physics and Astronomy and Department of Chemistry, University of Missouri, Columbia, MO 65211, USA
Weitao Zheng
State Key Laboratory of Automotive Simulation and Control, School of Materials Science and Engineering, Key Laboratory of Automobile Materials of MOE, Electron Microscopy Center, Jilin University, Changchun 130012, People’s Republic of China
Xiaoqiang Cui
State Key Laboratory of Automotive Simulation and Control, School of Materials Science and Engineering, Key Laboratory of Automobile Materials of MOE, Electron Microscopy Center, Jilin University, Changchun 130012, People’s Republic of China

Corresponding Author: Xiaoqiang Cui

xqcui@jlu.edu.cn

Nano-Micro Letters, Vol. 16 (2024), Article Number: 4

Abstract

Electrochemical carbon dioxide reduction reaction (CO2RR) involves a variety of intermediates with highly correlated reaction and ad-desorption energies, hindering optimization of the catalytic activity. For example, increasing the binding of the *COOH to the active site will generally increase the *CO desorption energy. Breaking this relationship may be expected to dramatically improve the intrinsic activity of CO2RR, but remains an unsolved challenge. Herein, we addressed this conundrum by constructing a unique atomic dispersed hetero-pair consisting of Mo-Fe di-atoms anchored on N-doped carbon carrier. This system shows an unprecedented CO2RR intrinsic activity with TOF of 3336 h−1, high selectivity toward CO production, Faradaic efficiency of 95.96% at − 0.60 V and excellent stability. Theoretical calculations show that the Mo-Fe diatomic sites increased the *COOH intermediate adsorption energy by bridging adsorption of *COOH intermediates. At the same time, d-d orbital coupling in the Mo-Fe di-atom results in electron delocalization and facilitates desorption of *CO intermediates. Thus, the undesirable correlation between these steps is broken. This work provides a promising approach, specifically the use of di-atoms, for breaking unfavorable relationships based on understanding of the catalytic mechanisms at the atomic scale.


Highlights:
1 A unique atomic dispersed hetero-pair was successfully synthesized, consisting of Mo-Fe di-atoms anchored on N-doped carbon carrier.
2 This strategy breaks the linear scaling relationships of electrocatalytic CO2 reduction by simultaneously regulating the *COOH adsorption energy and *CO desorption energy.
3 The as-prepared MoFe–N–C exhibits excellent performance for CO2RR to CO with a high turnover frequency (TOF) of 3336.21 h−1, CO Faradaic efficiency (FECO) of 95.96% at − 0.60 V (versus RHE) and outstanding stability.

Keywords

CO2 reduction reaction Atomic dispersed catalyst Hetero-diatomic pair Ad-desorption energy Linear scaling relation
Jin, Zhaoyong, Meiqi Yang, Yilong Dong, Xingcheng Ma, Ying Wang, Jiandong Wu, Jinchang Fan, Dewen Wang, Rongshen Xi, Xiao Zhao, Tianyi Xu, Jingxiang Zhao, Lei Zhang, David J. Singh, Weitao Zheng, and Xiaoqiang Cui. 2023. “Atomic Dispersed Hetero-Pairs for Enhanced Electrocatalytic CO2 Reduction”. Nano-Micro Letters 16 (November):4. https://doi.org/10.1007/s40820-023-01214-2.
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