Design of Local Atomic Environments in Single‐Atom Electrocatalysts for Renewable Energy Conversions

Abstract Single‐atom electrocatalysts (SAECs) have recently attracted tremendous research interest due to their often remarkable catalytic responses, unmatched by conventional catalysts. The electrocatalytic performance of SAECs is closely related to the specific metal species and their local atomic environments, including their coordination number, the determined structure of the coordination sites, and the chemical identity of nearest and second nearest neighboring atoms. The wide range of distinct chemical bonding configurations of a single‐metal atom with its surrounding host atoms creates virtually limitless opportunities for the rational design and synthesis of SAECs with tunable local atomic environment for high‐performance electrocatalysis. In this review, the authors first identify fundamental hurdles in electrochemical conversions and highlight the relevance of SAECs. They then critically examine the role of the local atomic structures, encompassing the first and second coordination spheres of the isolated metal atoms, on the design of high‐performance SAECs. The relevance of single‐atom dopants for host activation is also discussed. Insights into the correlation between local structures of SAECs and their catalytic response are analyzed and discussed. Finally, the authors summarize major challenges to be addressed in the field of SAECs and provide some perspectives in the rational construction of superior SAECs for a wide range of electrochemical conversions.