文献类型：期刊文献

英文题名：High Performance Pseudo-Pt@Pt Core-Shell Electrocatalyst for Oxygen Reduction Reaction: A Density Functional Theory Study

作者：Zhang, Yan-Ping[1,2];Wei, He-He[1,2];Wang, Zhi-Qiang[1,2];Hu, P.[1,2,3];Gong, Xue-Qing[1,2,4]

机构：[1]East China Univ Sci & Technol, Ctr Computat Chem, State Key Lab Green Chem Engn & Ind Catalysis, Shanghai 200237, Peoples R China;[2]East China Univ Sci & Technol, Res Inst Ind Catalysis, Sch Chem & Mol Engn, Shanghai 200237, Peoples R China;[3]ShanghaiTech Univ, Sch Phys Sci & Technol, Shanghai 201210, Peoples R China;[4]Shanghai Jiao Tong Univ, Sch Chem & Chem Engn, Shanghai 200240, Peoples R China

年份：2024

卷号：128

期号：37

起止页码：15476

外文期刊名：JOURNAL OF PHYSICAL CHEMISTRY C

收录：;EI(收录号：20243717020903);WOS:【SCI-EXPANDED(收录号:WOS:001308684400001)】；

基金：This work was supported by the National Key R&D Program of China (2021YFA1500700, 2023YFA1508500) and the National Natural Science Foundation of China (21825301, 92045303, 22203030).

语种：英文

外文关键词：Cobalt alloys - Copper alloys - Electrolysis - Electrolytic reduction - Lead alloys - Nickel alloys - Oxygen reduction reaction - Platinum

摘要：The development of cost-effective Pt-based oxygen reduction reaction (ORR) electrocatalysts is crucial for the application of proton exchange membrane fuel cells (PEMFCs). In this work, by using density functional theory calculations, we show that the Pt-M@Pt core-shell alloy (M = Co, Ni, Cu, with Pt-M alloy as the pseudo-Pt core and Pt as the shell) gives significantly higher ORR activity than pure Pt and common Pt-M alloys. Through structural and electronic analyses, we suggest that this is mainly caused by the asymmetric strain modulation effect of the pseudo-Pt core on the Pt shell and the interfacial charge transfer, which leads to a significant downward shift of the d-band center (epsilon d) and alters the bonding mode between the metal d orbitals and the adsorbed oxygen (O) p orbitals from equal contributions of the five d orbitals to dominant contributions of d(xy) and d(x2-y2) orbitals, thereby weakening the adsorption strength of O. Notably, the PtCo@Pt(111) surface with a suitable compressive strain and appropriate interfacial charge transfer exhibits the highest ORR activity and the corresponding overpotential is 0.38 V lower than Pt(111).