Heterostructured Mo2 C-MoOx on carbon cloth (Mo2 C-MoOx /CC), as a model of easily oxidized electrocatalysts under ambient conditions, is investigated to uncover surface reconfiguration during the hydrogen evolution reaction (HER). Raman spectroscopy combined with electrochemical tests demonstrates that the MoVI oxides on the surface are in situ reduced to MoIV , accomplishing promoted HER in acidic condition. As indicated by density functional theoretical calculations, the in situ reduced surface with terminal Mo=O moieties can effectively bring the negative ΔGH* on bare Mo2 C close to a thermodynamic neutral value, addressing difficult H* desorption toward fast HER kinetics. The optimized Mo2 C-MoOx /CC only requires a low overpotential (η10 ) of 60 mV at -10 mA cm-2 in 1.0 m HClO4 , outperforming Mo2 C/CC and most non-precious electrocatalysts. In situ surface reconfiguration are shown on W2 C-WOx , highlighting the significance to boost various metal-carbides and to identify active sites.
Keywords: heterointerfaces; hydrogen evolution reaction; in situ reconfiguration; molybdenum carbides; surface oxides.
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