Ultrathin N-Doped Mo₂C Nanosheets with Exposed Active Sites as Efficient Electrocatalyst for Hydrogen Evolution Reactions.

Abstract

Probing competent electrocatalysts for hydrogen evolution reaction (HER) of water splitting is one of the most hopeful approaches to confront the energy and environmental crisis. Herein, we highlight ultrathin N-doped Mo₂C nanosheets (N-Mo₂C NSs) in the role of greatly efficient platinum-free-based electrocatalysts for the HER. The transformation of crystal phase and structure between MoO₂ nanosheets with a thickness of ∼1.1 nm and N-Mo₂C NSs with a thickness of ∼1.0 nm is studied in detail. Structural analyses make clear that the surfaces of the N-Mo₂C NSs are absolutely encompassed by apical Mo atoms, hence affording an ideal catalyst prototype to expose the role of Mo atoms for the duration of HER catalysis. Theoretical calculations demonstrate that the nanosheet structure, N doping, and particular crystalline phase of Mo₂C produce more exposed Mo active sites, including Mo atoms on the C plane and doped N atoms. Through detailed electrochemical investigations, N-Mo₂C NSs possess HER activity with an onset potential of -48.3 mV vs RHE, Tafel slope of 44.5 mV dec^-1, and overpotential of 99 mV vs RHE at the cathodic current density of 10 mA cm^-2 with excellent long-term stability. Lastly, the calcination temperature and dicyandiamide amount can obviously affect the phase transformation and surface structure of molybdenum carbide, resulting in an adjustable HER activity. This synthesis mechanism will facilitate the understanding and optimization of Mo-based electrocatalysts in the energy conversion field.