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.

The Electronic Metal–Support Interaction Directing the Design of Single Atomic Site Catalysts: Achieving High Efficiency Towards Hydrogen Evolution

“…[17][18][19][20][21] The arise of single atomic site catalysts (SACs) brings new hope to the hydrogen industry. [22][23][24][25][26] Till now, many researches of SACs have been focused on the HER. [27][28][29][30][31][32][33] However, there is still some barrier on the way to apply the SACs in the practical hydrogen production.…”

Recent Advances in Electrode Design for Rechargeable Zinc–Air Batteries

“…The details about single-atom catalysts for ORR/ OER and ZABs have been well summarized elsewhere. [71]…”

Active site engineering of single-atom carbonaceous electrocatalysts for the oxygen reduction reaction

“…The central atom of various M-N-C electrocatalysts with different electronic structures will undoubtedly determine the ORR catalytic activity. [83][84][85] In the past decade, much progress has been made to reveal the intrinsic ORR activity of M-N-C electrocatalysts, following the order of Fe-N-C > Co-N-C > Cu-N-C > Mn-N-C > Ni-N-C. [86][87][88][89][90][91] Accordingly, the below sections will mainly focus on the Fe-N-C systems, examining the strategies for enhancing their intrinsic activity. According to the Sabatier principle, the adsorption of the ORR intermediates (i.e., O 2 *, OOH*, O* and OH*) on the active site should be neither too strong nor too weak.…”