Synergistically Tuning Surface States of Hierarchical MoC by Pt‐N Dual‐Doping Engineering for Optimizing Hydrogen Evolution Activity

Catalytic performance can be greatly enhanced by rational modulation of the surface state. In this study, reasonable adjustment of the surface states around the Fermi level (EF ) of molybdenum carbide (MoC) (α phase) via a Pt-N dual-doping process to fabricate an electrocatalyst named as Pt-N-MoC is performed to promote hydrogen evolution reaction (HER) performance over the MoC surface. Systematically experimental and theoretical analyses demonstrate that the synergistic tuning of Pt and N can cause the delocalization of surface states, with an increase in the density of surface states near the EF . This is beneficial for accumulating and transferring electrons between the catalyst surface and adsorbent, resulting in a positively linear correlation between the density of surface states near the EF and the HER activity. Moreover, the catalytic performance is further enhanced by artificially fabricating a Pt-N-MoC catalyst that has a unique hierarchical structure composed of MoC nanoparticles (0D), nanosheets (2D), and microrods (3D). As expected, the obtained Pt-N-MoC electrocatalyst exhibits superb HER activity with an extremely low overpotential of 39 mV@10 mA cm-2 as well as superb stability (over 24 d) in an alkaline solution. This work highlights a novel strategy to develop efficient electrocatalysts via adjusting their surface states.