Achieving Efficient CO<sub>2</sub> Electrolysis to CO by Local Coordination Manipulation of Nickel Single-Atom Catalysts
Zhaoyang Chen, Chuanhao Wang, Xian Zhong, Hao Lei, Jiawei Li, Yuan Ji, Chunxiao Liu, Mao Ding, Yizhou Dai, Li Xu, Tingting Zheng, Qiu Jiang, Hong‐Jie Peng, Chuan Xia
Abstract
Selective electroreduction of CO 2 to C 1 feed gas provides an attractive avenue to store intermittent renewable energy. However, most of the CO 2 -to-CO catalysts are designed from the perspective of structural reconstruction, and it is challenging to precisely design a meaningful confining microenvironment for active sites on the support. Herein, we report a local sulfur doping method to precisely tune the electronic structure of an isolated asymmetric nickel–nitrogen–sulfur motif (Ni 1 -NSC). Our Ni 1 -NSC catalyst presents >99% faradaic efficiency for CO 2 -to-CO under a high current density of −320 mA cm –2 . In situ attenuated total reflection surface-enhanced infrared absorption spectroscopy and differential electrochemical mass spectrometry indicated that the asymmetric sites show a significantly weaker binding strength of *CO and a lower kinetic overpotential for CO 2 -to-CO. Further theoretical analysis revealed that the enhanced CO 2 reduction reaction performance of Ni 1 -NSC was mainly due to the effectively decreased intermediate activation energy.