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Edge Segregated Polymorphism in 2D Molybdenum Carbide.

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Summary

Researchers grew diverse molybdenum carbide (Mo2C) crystals using a novel copper diffusion method. Controlling copper thickness yielded different crystal structures, including Bernal-stacked Mo2C, showing promise for catalysis.

Keywords:
MXenemolybdenum carbidephase engineeringscanning transmission electron microscopy

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Area of Science:

  • Materials Science
  • Solid-State Chemistry
  • Nanotechnology

Background:

  • Molybdenum carbide (Mo2C) is an important MXene with diverse polymorphs, but their growth conditions remain largely unknown.
  • Understanding the synthesis of different Mo2C phases is crucial for unlocking their full potential in various applications.

Purpose of the Study:

  • To investigate the controlled growth of molybdenum carbide (Mo2C) polymorphs and polytypes.
  • To explore the influence of diffusion barriers on crystal structure and stacking order.
  • To evaluate the catalytic performance of different Mo2C phases, particularly in the hydrogen evolution reaction (HER).

Main Methods:

  • Utilized a diffusion-mediated growth mechanism with liquid copper as a diffusion barrier between molybdenum and carbon precursors.
  • Controlled Mo2C crystal growth by adjusting the thickness of the copper diffusion barrier.
  • Employed density functional theory (DFT) calculations to analyze atomic structures and stacking transformations.
  • Experimentally verified catalytic activity in the hydrogen evolution reaction (HER).

Main Results:

  • Successfully grew Mo2C crystals with mixed polymorphs and polytypes.
  • Demonstrated control over crystal morphology, ranging from uniform AA-stacked T-phase Mo2C to "wedding cake"-like structures with predominant Bernal-stacked Mo2C.
  • DFT calculations revealed that Bernal-stacked Mo2C possesses a d band closer to the Fermi energy.
  • Bernal-stacked Mo2C exhibited promising catalytic performance in the hydrogen evolution reaction (HER).

Conclusions:

  • The diffusion-mediated growth mechanism using a liquid copper barrier allows for controlled synthesis of diverse Mo2C polymorphs and polytypes.
  • Crystal structure and stacking order can be tuned by controlling the copper barrier thickness.
  • Bernal-stacked Mo2C shows significant potential for catalytic applications, particularly in HER, due to its electronic structure.