Sub‐6 nm Fully Ordered L10‐Pt–Ni–Co Nanoparticles Enhance Oxygen Reduction via Co Doping Induced Ferromagnetism Enhancement and Optimized Surface Strain

By Tanyuan Wang, Jiashun Liang, Zhonglong Zhao, Shenzhou Li, G. Lu, Z. Xia, Chao Wang, Jiahuan Luo, Jiantao Han, Cheng Ma and 2 more. Advanced Energy Materials, 2019

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Engineering the crystal structure of Pt–M (M = transition metal) nanoalloys to chemically ordered ones has drawn increasing attention in oxygen reduction reaction (ORR) electrocatalysis due to their high resistance against M etching in acid. Although Pt–Ni alloy nanoparticles (NPs) have demonstrated respectable initial ORR activity in acid, their stability remains a big challenge due to the fast etching of Ni. In this work, sub‐6 nm monodisperse chemically ordered L10‐Pt–Ni–Co NPs are synthesized for the first time by employing a bifunctional core/shell Pt/NiCoOx precursor, which could provide abundant O‐vacancies for facilitated Pt/Ni/Co atom diffusion and prevent NP sintering during thermal annealing. Further, Co doping is found to remarkably enhance the ferromagnetism (room temperature coercivity reaching 2.1 kOe) and the consequent chemical ordering of L10‐Pt–Ni NPs. As a result, the best‐performing carbon supported L10‐PtNi0.8Co0.2 catalyst reveals a half‐wave potential (E1/2) of 0.951 V versus reversible hydrogen electrode in 0.1 m HClO4 with 23‐times enhancement in mass activity over the commercial Pt/C catalyst along with much improved stability. Density functional theory (DFT) calculations suggest that the L10‐PtNi0.8Co0.2 core could tune the surface strain of the Pt shell toward optimized Pt–O binding energy and facilitated reaction rate, thereby improving the ORR electrocatalysis.

Subfields: Electrical and Electronic Engineering, Renewable Energy, Sustainability and the Environment

View Paper: https://www.semanticscholar.org/paper/06151b1859232e8df5998f1de394ef0bb79eac22