Adapting Atomic Configuration Steers Dynamic Half-Occupied State for Efficient CO<sub>2</sub> Electroreduction to CO
Jiali Wang, Hui Tan, Chia‐Shuo Hsu, You‐Chiuan Chu, C.C. Chan, Kuan-Hsu Chen, Xuan-Rou Lin, Yi-Chun Lee, Hsiao‐Chien Chen, Hsiao-Chien Chen, Hao Ming Chen, Hao Ming Chen
Abstract
High Resolution Image Download MS PowerPoint Slide Electronic structures stand at the center to essentially understand the catalytic performance and reaction mechanism of atomically dispersed transition-metal–nitrogen–carbon catalysts (ADTCs). However, under realistic electrocatalytic conditions, the dynamic electronic disturbance at metal centers originating from complicated interactions with microenvironments is commonly neglected, which makes a true structure–property correlation highly ambiguous. Here, we employ operando time-resolved X-ray absorption spectroscopy to delve deeply into dynamic electronic behaviors of a family of transition-metal centers that are observed to adaptively vary in the metal–ligand configuration during the CO 2 electroreduction reaction. We identify dynamic electronic/geometric configuration and d-orbital occupation under working conditions, demonstrating an unprecedentedly precise activity descriptor, i.e., dynamic axial d z 2 electron, for the CO 2 -to-CO conversion. Direct results validate that the half-occupied state suggests the optimum binding behaviors with intermediates, significantly promoting CO production, which has been demonstrated by a significant kinetics enhancement of 1 to 2 orders of magnitude as compared with fully occupied and unoccupied states. This work presents the first empirical demonstration for a real correlation between the dynamic electronic/geometric configuration and catalytic kinetics in ADTCs, paving a new way for modulating catalysts and designing highly efficient reaction pathways.