DFT Study of Ni_m@Pt₁Au_n-m-1 (n=19, 38, 55, 79; m = 1, 6, 13, 19) Core-Shell ORR Catalyst

Authors

Wen-Jie Li, 1. State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology, Dalian 116024, Liaoning, China;
Dong-Xu Tian, 1. State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology, Dalian 116024, Liaoning, China;Follow
Hong Du, 1. State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology, Dalian 116024, Liaoning, China;
Xi-Qiang Yan, 2. Guangdong Key Laboratory for Hydrogen Energy Technologies, Foshan University, Foshan 528000, Guangdong, China;Follow

Corresponding Author

Dong-Xu Tian(tiandx@dlut.edu.cn);
Xi-Qiang Yan(965664856@qq.com)

Abstract

The slow kinetics of oxygen reduction reaction (ORR) limits the performance of low temperature fuel cells. Thus, it needs to design effective catalysts with low cost. Core-shell clusters (CSNCs) show promising activity because of their size-dependent geometric and electronic effects. The ORR activity trend of Ni_m@Pt₁Au_n-m-1(n = 19, 38, 55, 79; m = 1, 6, 13, 19) was studied using the GGA-PBE-PAW methods. The adsorption configurations of *O, *OH and *OOH were optimized and the reaction free energies of four proton electron (H⁺ + e^-) transfer steps were calculated. Using overpotential as a descriptor for the catalytic activity, Ni₆@Pt₁Au₃₁ was found to be the most active ORR catalyst. Ni₁@Pt₁Au₁₇, Ni₁₃@Pt₁Au₄₁, and Ni₁₉@Pt₁Au₅₉ had better activity than pure Pt clusters and Pt(111). Bader charge and DOS data indicate that the single Pt atom embedded on Ni_m@Au_n-m can tune the electronic property of active site, and thus, significantly improve the activity. The present study showed that the single Pt atom embedded on Ni_m@Au_n-m is a rational strategy to design effective core-shell ORR catalysts.

Graphical Abstract

Keywords

core-shell metal clusters, oxygen reduction reaction, density functional theory, overpotential, single atom catalysis

DOI Link

https://doi.org/10.13208/j.electrochem.210329

Publication Date

2021-08-28

Online Available Date

2021-06-09

Revised Date

2021-05-08

Received Date

2021-03-27

Recommended Citation

Wen-Jie Li, Dong-Xu Tian, Hong Du, Xi-Qiang Yan. DFT Study of Ni_m@Pt₁Au_n-m-1 (n=19, 38, 55, 79; m = 1, 6, 13, 19) Core-Shell ORR Catalyst[J]. Journal of Electrochemistry, 2021 , 27(4): 357-365.
DOI: The slow kinetics of oxygen reduction reaction (ORR) limits the performance of low temperature fuel cells. Thus, it needs to design effective catalysts with low cost. Core-shell clusters (CSNCs) show promising activity because of their size-dependent geometric and electronic effects. The ORR activity trend of Ni_m@Pt₁Au_n-m-1(n = 19, 38, 55, 79; m = 1, 6, 13, 19) was studied using the GGA-PBE-PAW methods. The adsorption configurations of *O, *OH and *OOH were optimized and the reaction free energies of four proton electron (H⁺ + e^-) transfer steps were calculated. Using overpotential as a descriptor for the catalytic activity, Ni₆@Pt₁Au₃₁ was found to be the most active ORR catalyst. Ni₁@Pt₁Au₁₇, Ni₁₃@Pt₁Au₄₁, and Ni₁₉@Pt₁Au₅₉ had better activity than pure Pt clusters and Pt(111). Bader charge and DOS data indicate that the single Pt atom embedded on Ni_m@Au_n-m can tune the electronic property of active site, and thus, significantly improve the activity. The present study showed that the single Pt atom embedded on Ni_m@Au_n-m is a rational strategy to design effective core-shell ORR catalysts.