Computational exploration of two-dimensional vacancy-free boridene sheet and its derivatives: high stabilities and the promise for hydrogen evolution reaction

Abstract

The recent synthesis of a two-dimensional (2D) MBene sheet, referred to as the boridene sheet (Mo₄B₆T_z), has ignited considerable interest in exploring 2D transition metal borides. Boridene has an ordered arrangement of metal vacancies, which are pivotal to its stability. Employing first-principles calculations, we explored the stable phases, electronic properties and catalytic abilities of boridene with different vacancy concentrations (V_m). Our results demonstrate that V_m significantly influences the cohesive energies of boridene sheets. Phonon spectrum and ab initio molecular dynamics simulations reveal the high stability of the vacancy-free boridene Mo₆B₆T₆ (T = O, -OH), underscoring their potential for experimental realization. Substituting Mo atoms with Nb, Ta, or W enhances the structural stability of boridene sheets, leading to the identification of four stable variants: Nb₆B₆F₆, Ta₆B₆F₆, Ta₆B₆O₆, and W₆B₆O₆. These boridene sheets exhibit metallic behavior, with five structures displaying near-zero Gibbs free energy for hydrogen atom adsorption, indicating their potential as catalysts for the hydrogen evolution reaction. The uncovering of vacancy-free boridenes and their 2D derivatives greatly broadens the scope of the MBene family.

Keywords

2D materials / boridene / first-principles calculations / hydrogen evolution reaction

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