Achieving Efficient CO<sub>2</sub> Electrolysis to CO by Local Coordination Manipulation of Nickel Single-Atom Catalysts.

Chen, Zhaoyang; Wang, Chuanhao; Zhong, Xian; Lei, Hao; Li, Jiawei; Ji, Yuan; Liu, Chunxiao; Ding, Mao et al. · Nano Lett · 2023

basic_science · Level V

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Abstract

Selective electroreduction of CO<sub>2</sub> to C<sub>1</sub> feed gas provides an attractive avenue to store intermittent renewable energy. However, most of the CO<sub>2</sub>-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<sub>1</sub>-NSC). Our Ni<sub>1</sub>-NSC catalyst presents >99% faradaic efficiency for CO<sub>2</sub>-to-CO under a high current density of -320 mA cm<sup>-2</sup>. <i>In situ</i> 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<sub>2</sub>-to-CO. Further theoretical analysis revealed that the enhanced CO<sub>2</sub> reduction reaction performance of Ni<sub>1</sub>-NSC was mainly due to the effectively decreased intermediate activation energy.