Dual-Metal Active Sites Mediated by p-Block Elements: Knowledge-Driven Design of Oxygen Reduction Reaction Catalysts

Pengyue Shan; Xue Bai; Qi Jiang; Yunjian Chen; Yazhou Wang; Tong Liu; Hong Cui; Rong Feng; Qin Kang; Zhiyong Liang; Hongkuan Yuan

doi:10.1021/acsomega.2c01415

Dual-Metal Active Sites Mediated by p-Block Elements: Knowledge-Driven Design of Oxygen Reduction Reaction Catalysts

ACS Omega. 2022 Jun 3;7(23):19676-19686. doi: 10.1021/acsomega.2c01415. eCollection 2022 Jun 14.

Authors

Pengyue Shan^{1

2}, Xue Bai^{1

2}, Qi Jiang^{1

2}, Yunjian Chen^{1

2}, Yazhou Wang^{1

2}, Tong Liu^{1

2}, Hong Cui^{1

2}, Rong Feng^{1

2}, Qin Kang^{1

2}, Zhiyong Liang^{1

2}, Hongkuan Yuan³

Affiliations

¹ School of Mechanical Engineering, Shaanxi University of Technology, Hanzhong, Shaanxi 723001, China.
² Shaanxi Key Laboratory of Industrial Automation, Shaanxi University of Technology, Hanzhong, Shaanxi 723001, China.
³ School of Physical Science and Technology, Southwest University, Chongqing 400715, China.

Abstract

In this study, the oxygen reduction reaction (ORR) process of dual-metal active site catalysts (FeMN₆-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 FeMN₆-Gra (M = Mn, Ni, Co, or Cu) catalysts exhibit higher catalytic performance than their undoped counterparts. Among the investigated catalysts, FeNiN₆-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 H₂O) in the FeNiN₆B1-Gra-catalyzed ORR process is 0.17 eV, which is smaller than that of the FeNiN₆-Gra-catalyzed process (0.28 eV). Overall, the results demonstrate that B-doping can improve the activity of FeMN₆-Gra catalysts and provide a new method for the future development of efficient electrocatalysts.