An Ultrasmall Ordered High-Entropy Intermetallic with Multiple Active Sites for the Oxygen Reduction Reaction

Tao Chen; Chunyu Qiu; Xinkai Zhang; Hangchao Wang; Jin Song; Kun Zhang; Tonghuan Yang; Yuxuan Zuo; Yali Yang; Chuan Gao; Wukun Xiao; Zewen Jiang; Yucheng Wang; Yan Xiang; Dingguo Xia

doi:10.1021/jacs.3c12649

An Ultrasmall Ordered High-Entropy Intermetallic with Multiple Active Sites for the Oxygen Reduction Reaction

J Am Chem Soc. 2024 Jan 10;146(1):1174-1184. doi: 10.1021/jacs.3c12649. Epub 2023 Dec 28.

Authors

Tao Chen¹, Chunyu Qiu², Xinkai Zhang³, Hangchao Wang¹, Jin Song¹, Kun Zhang¹, Tonghuan Yang¹, Yuxuan Zuo¹, Yali Yang¹, Chuan Gao¹, Wukun Xiao¹, Zewen Jiang¹, Yucheng Wang², Yan Xiang³, Dingguo Xia¹

Affiliations

¹ Beijing Key Laboratory of Theory and Technology for Advanced Batteries Materials, School of Materials Science and Engineering, Peking University, Beijing 100871, P.R. China.
² State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China.
³ Beijing Key Laboratory of Bio-inspired Energy Materials and Devices, School of Space and Environment, Beihang University, Beijing 100191, China.

Abstract

Controlling multimetallic ensembles at the atomic level is significantly challenging, particularly for high-entropy alloys with more than five elements. Herein, we report an innovative ultrasmall (∼2 nm) PtFeCoNiCuZn high-entropy intermetallic (PFCNCZ-HEI) with a well-ordered structure synthesized by using the space-confined strategy. By exploiting these combined metals, the PFCNCZ-HEI nanoparticles achieve an ultrahigh mass activity of 2.403 A mg_Pt^-1 at 0.90 V vs reversible hydrogen electrode for the oxygen reduction reaction, which is up to 19-fold higher than that of state-of-the-art commercial Pt/C. A proton exchange membrane fuel cell assembled with PFCNCZ-HEI as the cathode (0.03 mg_Pt cm^-2) exhibits a power density of 1.4 W cm^-2 and a high mass-normalized rated power of 45 W mg_Pt^-1. Furthermore, theoretical calculations reveal that the outer electrons of the non-noble-metal atoms on the surface of the PFCNCZ-HEI nanoparticle are modulated to show characteristics of multiple active centers. This work offers a promising catalyst design direction for developing highly ordered HEI nanoparticles for electrocatalysis.