Electronic and geometric modulations of catalysts for electrochemical CO2 reduction reaction

Abstract

The electrocatalytic CO₂ reduction reaction (CO₂RR) converts CO₂ into high-value-added chemicals using clean and renewable energy, making it one of the most promising strategies for addressing present-day energy and environmental crises. Electrocatalysts play a crucial role in electrocatalytic CO₂RR systems because they determine catalytic activities and selectivities. Electronic and geometric structures are two important factors that affect the electrocatalytic performances of electrocatalysts, in which the electronic structures are related to the adsorption strengths of substrates/intermediates while the geometric structures are associated with the microenvironments of catalytic reactions. Consequently, modulating the electronic and/or geometric structures of electrocatalysts can significantly improve the catalytic performances. To better understand the roles and importance of electronic and geometric structural modulations, this review systematically summarizes and discusses the latest progress of these two strategies that apply to electrocatalytic CO₂RRs. First, the methods for electronic and geometric structural modulations of electrocatalysts are introduced. Then, the trends and mechanisms of electronic structural modulation of various metal elements are explored in detail based on element partitioning across the periodic table, starting with the s- and p-block elements and ending with broad coverage of the d- and f-block metals, and the advantages and functions of geometric structural modulation of catalyst supports and the impact mechanism on performance are discussed according to types of supports. Finally, some prospects are proposed to provide suggestions for designing more efficient electrocatalysts for the electrocatalytic CO₂RR based on these two strategies.