Proximity Electronic Effect of Ni/Co Diatomic Sites for Synergistic Promotion of Electrocatalytic Oxygen Reduction and Hydrogen Evolution

作者：Min Li, Houyu Zhu, Qing Yuan, Tuya Li, Minmin Wang, Peng Zhang, Yilin Zhao, Donglin Qin, Wenyue Guo, Bin Liu, Xuan Yang, Yunqi Liu, Yuan Pan · 发表于：Advanced Functional Materials · 年份：2022 · DOI：10.1002/adfm.202210867 · 被引用次数：245 · 研究领域：Electrocatalysts for Energy Conversion、Electrochemical Analysis and Applications、Fuel Cells and Related Materials

Abstract The modulation effect manifests an encouraging potential to enhance the performance of single‐atom catalysts; however, the in‐depth study about this effect for the isolated diatomic sites (DASs) remains a great challenge. Herein, a proximity electronic effect (PEE) of Ni/Co DASs is proposed that is anchored in N‐doped carbon (N‐C) substrate (NiCo DASs/N‐C) for synergistic promoting electrocatalytic oxygen reduction reaction (ORR) and hydrogen evolution reaction (HER). Benefiting from the PEE of adjacent Ni anchored by four nitrogen (Ni‐N 4 ) moiety, NiCo DASs/N‐C catalyst exhibits superior ORR and HER activity. In situ characterization results suggest Co anchored by four nitrogen (Co‐N 4 ) as main active site for O 2 adsorption‐activation process, which promotes the formation of key *OOH and the desorption of *OH intermediate to accelerate the multielectron reaction kinetics. Theoretical calculation reveals the adjacent Ni‐N 4 site as a modulator can effectively adjust the electronic localization of proximity Co‐N 4 site, promoting the *OH desorption and *H adsorption on Co‐N 4 site, thereby boosting ORR and HER process significantly. This study opens a new opportunity for rationally regulating the electronic localization of catalytic active centers by proximity single‐atom moiety, as well as provides guidance for designing high‐efficiency bifunctional electrocatalysts for promising applications.