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High-Performance MoC Electrocatalyst for Hydrogen Evolution Reaction Enabled by Surface Sulfur Substitution.

Xiangyong Zhang1,2, Tianying Liu1,2,3, Ting Guo1,2

  • 1School of Materials Science and Engineering, Central South University, Changsha 410083, China.

ACS Applied Materials & Interfaces
|August 18, 2021
PubMed
Summary

Sulfur doping enhances molybdenum carbide (MoC) electrocatalysts for the hydrogen evolution reaction (HER). This modification optimizes active sites and electronic structure, leading to superior catalytic performance and overcoming previous limitations.

Keywords:
electrocatalysthydrogen evolution reactionmolybdenum carbidesulfur substitutionsurface engineering

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Area of Science:

  • Materials Science
  • Electrochemistry
  • Catalysis

Background:

  • Molybdenum carbides (MoC) show promise as hydrogen evolution reaction (HER) catalysts due to electronic similarities with platinum-group metals.
  • A key limitation of MoC catalysts is their insufficient hydrogen adsorption capability, hindering practical application.
  • Surface reconstruction strategies are explored to enhance MoC catalytic activity.

Purpose of the Study:

  • To design a novel MoC-based electrocatalyst with improved HER performance.
  • To investigate the effect of sulfur doping on MoC's surface structure and electronic properties.
  • To address the hydrogen adsorption limitations of MoC for efficient HER.

Main Methods:

  • Density functional theory (DFT) calculations guided the catalyst design.
  • Synthesis of sulfur-doped molybdenum carbide electrocatalysts.
  • Electrochemical characterization of HER performance, including Tafel slope analysis.

Main Results:

  • Sulfur doping significantly increased the number of active sites and intrinsic activity of MoC.
  • Optimized electronic structure and improved electron transfer efficiency were observed.
  • The sulfur-substituted MoC exhibited superior HER performance with a Tafel slope of 48 mV dec-1, indicating efficient hydrogen evolution.

Conclusions:

  • Sulfur doping is an effective strategy for surface reconstruction of MoC electrocatalysts.
  • The terminal sulfur atoms critically facilitate near-zero hydrogen adsorption energy (ΔGH*) and a lower hydrogen release barrier.
  • The developed sulfur-doped MoC demonstrates a promising alternative for efficient hydrogen evolution catalysis.