Electronic Structure Design of Transition Metal-Based Catalysts for Electrochemical Carbon Dioxide Reduction

Abstract

With the increasingly serious greenhouse effect, the electrochemical carbon dioxide reduction reaction (CO₂RR) has garnered widespread attention as it is capable of leveraging renewable energy to convert CO₂ into value-added chemicals and fuels. However, the performance of CO₂RR can hardly meet expectations because of the diverse intermediates and complicated reaction processes, necessitating the exploitation of highly efficient catalysts. In recent years, with advanced characterization technologies and theoretical simulations, the exploration of catalytic mechanisms has gradually deepened into the electronic structure of catalysts and their interactions with intermediates, which serve as a bridge to facilitate the deeper comprehension of structure-performance relationships. Transition metal-based catalysts (TMCs), extensively applied in electrochemical CO₂RR, demonstrate substantial potential for further electronic structure modulation, given their abundance of d electrons. Herein, we discuss the representative feasible strategies to modulate the electronic structure of catalysts, including doping, vacancy, alloying, heterostructure, strain, and phase engineering. These approaches profoundly alter the inherent properties of TMCs and their interaction with intermediates, thereby greatly affecting the reaction rate and pathway of CO₂RR. It is believed that the rational electronic structure design and modulation can fundamentally provide viable directions and strategies for the development of advanced catalysts toward efficient electrochemical conversion of CO₂ and many other small molecules.

Keywords: active site; carbon dioxide reduction; carbon neutral; clean energy; d band center; electrocatalysts; electronic structure; energy conversion; selectivity; transition metal-based catalysts.