Two-Dimensional High-Entropy Metal Phosphorus Trichalcogenides for Enhanced Hydrogen Evolution Reaction

Ran Wang; Jinzhen Huang; Xinghong Zhang; Jiecai Han; Zhihua Zhang; Tangling Gao; Lingling Xu; Shengwei Liu; Ping Xu; Bo Song

doi:10.1021/acsnano.2c01064

Two-Dimensional High-Entropy Metal Phosphorus Trichalcogenides for Enhanced Hydrogen Evolution Reaction

ACS Nano. 2022 Mar 22;16(3):3593-3603. doi: 10.1021/acsnano.2c01064. Epub 2022 Feb 25.

Authors

Ran Wang¹, Jinzhen Huang¹, Xinghong Zhang¹, Jiecai Han¹, Zhihua Zhang², Tangling Gao³, Lingling Xu⁴, Shengwei Liu⁵, Ping Xu⁶, Bo Song¹

Affiliations

¹ National Key Laboratory of Science and Technology on Advanced Composites in Special Environments, Harbin Institute of Technology, Harbin150001, China.
² School of Materials Science and Engineering, Dalian Jiaotong University, Dalian116028, China.
³ Institute of Petrochemistry, Heilongjiang Academy of Sciences, Harbin150040, China.
⁴ Key Laboratory of Photonic and Electronic Bandgap Materials, Ministry of Education, School of Physics and Electronic Engineering, Harbin Normal University, Harbin150080, China.
⁵ School of Environmental Science and Engineering, Guangdong Provincial Key Laboratory of Environmental Pollution Control and Remediation Technology, Sun Yat-sen University, Guangzhou510006, China.
⁶ MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin150001, China.

PMID: 35212217
DOI: 10.1021/acsnano.2c01064

Abstract

Developing earth-abundant and highly effective electrocatalysts for hydrogen evolution reaction (HER) is a prerequisite for the upcoming hydrogen energy society. Two-dimensional (2D) high-entropy metal phosphorus trichalcogenides (MPCh₃) have the advantages of both near-continuous adsorption energies of high-entropy alloys (HEAs) and large specific surface area of 2D materials, which are excellent catalytic platforms. As a typical 2D high-entropy catalyst, Co_0.6(VMnNiZn)_0.4PS₃ nanosheets with high-concentration active sites are successfully demonstrated to show enhanced HER performance: an overpotential of 65.9 mV at a current density of 10 mA cm^-2 and a Tafel slope of 65.5 mV dec^-1. Decent spectroscopy characterizations are combined with density function theory analyses to show the scenario for the enhancement mechanism by a high-entropy strategy. The optimized S sites on the edge and P sites on the basal plane provide more active sites for hydrogen adsorption, and the introduced Mn sites boost water dissociation during the Volmer step. Two-dimensional high-entropy MPCh₃ provides an avenue for the combination of HEAs and 2D materials to enhance the HER performance, which also provides an alternative materials platform to explore and design superior catalysts for various electrochemical systems.

Keywords: 2D materials; electrocatalysis; high-entropy; hydrogen evolution reaction; metal phosphorus trichalcogenides.