Open AccessDual-Metal Active Sites Mediated by p-Block Elements: Knowledge-Driven Design of Oxygen Reduction Reaction Catalysts
Author(s) -
Pengyue Shan,
Xue Bai,
Qi Jiang,
Yunjian Chen,
Shaobin Wang,
Tong Liu,
HongLing Cui,
Rong Feng,
Qin Kang,
Zhiyong Liang,
Hongkuan Yuan
Publication year - 2022
Publication title -
acs omega
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.779
H-Index - 40
ISSN - 2470-1343
DOI - 10.1021/acsomega.2c01415
Subject(s) - catalysis , gibbs free energy , density functional theory , transition metal , metal , doping , adsorption , chemistry , oxygen reduction reaction , oxygen , inorganic chemistry , materials science , computational chemistry , electrode , thermodynamics , electrochemistry , organic chemistry , physics , optoelectronics
In this study, the oxygen reduction reaction (ORR) process of dual-metal active site catalysts (FeMN 6 -Gra, M = Mn, Ni, Co, or Cu) mediated by p-block elements was investigated using density functional theory calculations. The obtained results demonstrate that, in most cases, the B-doped FeMN 6 -Gra (M = Mn, Ni, Co, or Cu) catalysts exhibit higher catalytic performance than their undoped counterparts. Among the investigated catalysts, FeNiN 6 -Gra doping by B modulates the adsorption strength of the metal center on the oxygen-containing intermediates, showing the largest increase in the onset potential (from 0.66 to 0.94 V). Importantly, we found a new law that B-doping affects the total charge of the metal adsorption site and the four surrounding N atoms and that there is a linear relationship between the total charge and the Gibbs free energy. Transition state analysis shows that the energy barrier of the thermodynamic rate-determining step (*OH hydrogenation to H 2 O) in the FeNiN 6 B1-Gra-catalyzed ORR process is 0.17 eV, which is smaller than that of the FeNiN 6 -Gra-catalyzed process (0.28 eV). Overall, the results demonstrate that B-doping can improve the activity of FeMN 6 -Gra catalysts and provide a new method for the future development of efficient electrocatalysts.