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Area of Science:

  • Materials Science
  • Electrochemistry
  • Catalysis

Background:

  • Ammonia synthesis is crucial for global agriculture and industry.
  • Developing efficient electro-catalysts for nitrogen reduction is a key challenge.
  • Molybdenum carbide (MoC) is explored as a potential electro-catalyst.

Purpose of the Study:

  • Investigate the viability of cubic MoC as an electro-catalyst for ammonia synthesis.
  • Analyze nitrogen electroreduction and hydrogen evolution reactions on MoC surfaces.
  • Determine optimal conditions for efficient nitrogen reduction.

Main Methods:

  • Density functional theory (DFT) calculations were employed.
  • Free energy diagrams for associative and dissociative Heyrovsky mechanisms were analyzed.
  • Kinetic volcano plots for hydrogen evolution were generated.

Main Results:

  • Nitrogen reduction to ammonia can occur via an associative mechanism on MoC(111) at -0.3 V vs. SHE.
  • The MoC(110) surface exhibits a high rate for hydrogen evolution, potentially competing with nitrogen reduction.
  • Hydrogen adsorption competes with nitrogen adsorption on most MoC surfaces, except MoC(111).

Conclusions:

  • Cubic MoC is a potential electro-catalyst for ammonia synthesis.
  • Optimizing MoC surfaces, particularly MoC(111), is key for efficient nitrogen reduction.
  • Introducing carbon vacancies in MoC enhances nitrogen binding and suppresses hydrogen evolution, improving catalytic performance.