Abstract
Molybdenum carbide (Mo2C), a class of unterminated MXene, is endowed with rich polymorph chemistry, but the growth conditions of the various polymorphs are not understood. Other than the most commonly observed T‐phase Mo2C, little is known about other phases. Here, Mo2C crystals are successfully grown consisting of mixed polymorphs and polytypes via a diffusion‐mediated mechanism, using liquid copper as the diffusion barrier between the elemental precursors of Mo and C. By controlling the thickness of the copper diffusion barrier layer, the crystal growth can be controlled between a highly uniform AA‐stacked T‐phase Mo2C and a “wedding cake” like Mo2C crystal with spatially delineated zone in which the Bernal‐stacked Mo2C predominate. The atomic structures, as well as the transformations between distinct stackings, are simulated and analyzed using density functional theory (DFT)‐based calculations. Bernal‐stacked Mo2C has a d band closer to the Fermi energy, leading to a promising performance in catalysis as verified in hydrogen evolution reaction (HER).
