Design of Efficient Oxygen Reduction Reaction Catalysts with Single Transition Metal Atom on N‑Doped Graphdiyne

• Published in: The journal of physical chemistry letters 2023-11, Vol.14 (43), p.9624-9632
• Main Authors: Zou, Min, Yang, Jing, Yue, Xiaolong, Yuan, Yanan, Che, Zhongmei, Li, Mei, Li, Bo, Cui, Jiaxi, Hu, Wei, Wang, Shuai, Jiang, Jun, Jia, Chuanyi
• Format: Article
• Language: English
• Subjects: Physical Insights into Chemistry, Catalysis, and Interfaces
• ISSN: 1948-7185; 1948-7185
• DOI: 10.1021/acs.jpclett.3c02649

The revelation of the underlying structure–property relationship of single-atom catalysts (SACs) is a fundamental issue in the oxygen reduction reaction (ORR). Here we present systematic theoretical and experimental investigations of various N-doped graphdiyne (NGDY) supported transition metals (TMs) to shed light on this relationship. Calculation results indicate that the TMs’ comprehensive activities follow the order of Pd@NGDY > Ni@NGDY > Co@NGDY > Fe@NGDY, which fits well with our experimental conclusion. Moreover, detailed structure–property relationship (194 in total) analysis suggests that the key-species binding stability (ΔG *OH), the d-orbital center (εd/εd‑a) and charge transfer (ΔQTM/ΔQTM‑a) of the active metal before/after reactants adsorption and the bond length of TM-O (LTM‑O) as descriptors can well reflect the intermediate binding stability or ORR activity on different TM-SACs. Specifically, the change trend of catalytic activity is opposite to that of intermediate binding stability, meaning that too strongly bonded *OOH, *O, and *OH intermediates are unfavorable for ORR.