Boosting Electrocatalytic Carbon Dioxide Reduction via Self-Relaxation of Asymmetric Coordination in Fe-Based Single Atom Catalyst
Zhaoyong Jin
School of Materials Science and Engineering, Key Laboratory of Automobile Materials of MOE, Electron Microscopy Center, Jilin University, 130012 Changchun, China
These authors contributed equally to this work.
Search for more papers by this authorDongxu Jiao
School of Materials Science and Engineering, Key Laboratory of Automobile Materials of MOE, Electron Microscopy Center, Jilin University, 130012 Changchun, China
These authors contributed equally to this work.
Search for more papers by this authorYilong Dong
School of Materials Science and Engineering, Key Laboratory of Automobile Materials of MOE, Electron Microscopy Center, Jilin University, 130012 Changchun, China
Search for more papers by this authorLin Liu
School of Materials Science and Engineering, Key Laboratory of Automobile Materials of MOE, Electron Microscopy Center, Jilin University, 130012 Changchun, China
Search for more papers by this authorJinchang Fan
School of Materials Science and Engineering, Key Laboratory of Automobile Materials of MOE, Electron Microscopy Center, Jilin University, 130012 Changchun, China
Search for more papers by this authorMing Gong
School of Materials Science and Engineering, Key Laboratory of Automobile Materials of MOE, Electron Microscopy Center, Jilin University, 130012 Changchun, China
Search for more papers by this authorXingcheng Ma
School of Materials Science and Engineering, Key Laboratory of Automobile Materials of MOE, Electron Microscopy Center, Jilin University, 130012 Changchun, China
Search for more papers by this authorYing Wang
School of Materials Science and Engineering, Key Laboratory of Automobile Materials of MOE, Electron Microscopy Center, Jilin University, 130012 Changchun, China
Search for more papers by this authorWei Zhang
School of Materials Science and Engineering, Key Laboratory of Automobile Materials of MOE, Electron Microscopy Center, Jilin University, 130012 Changchun, China
Search for more papers by this authorCorresponding Author
Prof. Lei Zhang
College of Chemistry, Jilin University, 130012 Changchun, China
Search for more papers by this authorProf. Dr. Zhi Gen Yu
Institute of High Performance Computing (IHPC), Agency for Science, Technology and Research (A*STAR), 1 Fusionopolis Way, #16-16 Connexis, 138632 Singapore, Singapore
Search for more papers by this authorProf. Dr. Damien Voiry
Institut Européen des Membranes, IEM, UMR 5635, Université Montpellier, ENSCM, CNRS, 34000 Montpellier, France
Search for more papers by this authorCorresponding Author
Weitao Zheng
School of Materials Science and Engineering, Key Laboratory of Automobile Materials of MOE, Electron Microscopy Center, Jilin University, 130012 Changchun, China
Search for more papers by this authorCorresponding Author
Prof. Dr. Xiaoqiang Cui
School of Materials Science and Engineering, Key Laboratory of Automobile Materials of MOE, Electron Microscopy Center, Jilin University, 130012 Changchun, China
Search for more papers by this authorZhaoyong Jin
School of Materials Science and Engineering, Key Laboratory of Automobile Materials of MOE, Electron Microscopy Center, Jilin University, 130012 Changchun, China
These authors contributed equally to this work.
Search for more papers by this authorDongxu Jiao
School of Materials Science and Engineering, Key Laboratory of Automobile Materials of MOE, Electron Microscopy Center, Jilin University, 130012 Changchun, China
These authors contributed equally to this work.
Search for more papers by this authorYilong Dong
School of Materials Science and Engineering, Key Laboratory of Automobile Materials of MOE, Electron Microscopy Center, Jilin University, 130012 Changchun, China
Search for more papers by this authorLin Liu
School of Materials Science and Engineering, Key Laboratory of Automobile Materials of MOE, Electron Microscopy Center, Jilin University, 130012 Changchun, China
Search for more papers by this authorJinchang Fan
School of Materials Science and Engineering, Key Laboratory of Automobile Materials of MOE, Electron Microscopy Center, Jilin University, 130012 Changchun, China
Search for more papers by this authorMing Gong
School of Materials Science and Engineering, Key Laboratory of Automobile Materials of MOE, Electron Microscopy Center, Jilin University, 130012 Changchun, China
Search for more papers by this authorXingcheng Ma
School of Materials Science and Engineering, Key Laboratory of Automobile Materials of MOE, Electron Microscopy Center, Jilin University, 130012 Changchun, China
Search for more papers by this authorYing Wang
School of Materials Science and Engineering, Key Laboratory of Automobile Materials of MOE, Electron Microscopy Center, Jilin University, 130012 Changchun, China
Search for more papers by this authorWei Zhang
School of Materials Science and Engineering, Key Laboratory of Automobile Materials of MOE, Electron Microscopy Center, Jilin University, 130012 Changchun, China
Search for more papers by this authorCorresponding Author
Prof. Lei Zhang
College of Chemistry, Jilin University, 130012 Changchun, China
Search for more papers by this authorProf. Dr. Zhi Gen Yu
Institute of High Performance Computing (IHPC), Agency for Science, Technology and Research (A*STAR), 1 Fusionopolis Way, #16-16 Connexis, 138632 Singapore, Singapore
Search for more papers by this authorProf. Dr. Damien Voiry
Institut Européen des Membranes, IEM, UMR 5635, Université Montpellier, ENSCM, CNRS, 34000 Montpellier, France
Search for more papers by this authorCorresponding Author
Weitao Zheng
School of Materials Science and Engineering, Key Laboratory of Automobile Materials of MOE, Electron Microscopy Center, Jilin University, 130012 Changchun, China
Search for more papers by this authorCorresponding Author
Prof. Dr. Xiaoqiang Cui
School of Materials Science and Engineering, Key Laboratory of Automobile Materials of MOE, Electron Microscopy Center, Jilin University, 130012 Changchun, China
Search for more papers by this authorGraphical Abstract
We implemented an asymmetric coordination Fe−S1N3 SAC with significant geometric distortion. The Fe−S1N3 sites demonstrate distinctive self-relaxation behavior in response to different adsorption intermediates during the CO2RR process. The dynamic change in bond length enabled independent regulation of the *COOH and *CO intermediates adsorption energies, effectively breaking the linear scale relationship and enhancing the intrinsic activity.
Abstract
Addressing the limitations arising from the consistent catalytic behavior observed for various intermediates during the electrochemical carbon dioxide reduction reaction (CO2RR) poses a significant challenge in the optimization of catalytic activity. In this study, we aimed to address this challenge by constructing an asymmetric coordination Fe single atom catalyst (SCA) with a dynamically evolved structure. Our catalyst, consisting of a Fe atom coordinated with one S atom and three N atoms (Fe−S1N3), exhibited exceptional selectivity (CO Faradaic efficiency of 99.02 %) and demonstrated a high intrinsic activity (TOF of 7804.34 h−1), and remarkable stability. Using operando XAFS spectra and Density Functional Theory (DFT) calculations, we elucidated the self-relaxation of geometric distortion and dynamic evolution of bond lengths within the catalyst. These structure changes enabled independent regulation of the *COOH and *CO intermediate adsorption energies, effectively breaking the linear scale relationship and enhancing the intrinsic activity of CO2RR. This study provides valuable insights into the dynamic evolution of SACs and paves the way for targeted catalyst designs aimed to disrupt the linear scaling relationships.
Conflict of interest
The authors declare no conflict of interest.
Open Research
Data Availability Statement
The data that support the findings of this study are available in the supplementary material of this article.
Supporting Information
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