Engineering a Ce Promoter into a Three-Dimensional Porous MoC@NC Heterostructure for Hydrogen Evolution Electrocatalysis via Weakening the Mo-H Bond Strength.

The pursuit of highly efficient electrocatalysts for the alkaline hydrogen evolution reaction (HER) is of paramount importance for water splitting. However, it is still a formidable task in MoC-based materials because of the agglomeration and strong Mo-H binding of MoC units. Herein, a novel CeOCl-CeO/MoC heterostructure nesting within a three-dimensional porous nitrogen-doped carbon matrix has been designed and used for catalyzing HER via simultaneous morphology and heterointerface engineering. As expected, the optimal CeOCl-CeO(0.2)/MoC@3DNC exhibits impressive HER activity, with a low overpotential of 156 mV at a current density of 10 mA cm coupled with a slight Tafel slope of 62.20 mV dec. Introducing a Ce promoter, that is CeOCl and CeO, would endow the interface with an internal electric field and electron redistribution between CeOCl-CeO and MoC induced by the heterogeneous work function difference. Moreover, experimental investigation and density functional calculations confirm that the CeOCl-CeO/MoC heterointerface can downshift the d-band center of the active Mo center, weakening the strength of the Mo-H coupling. This proposed concept, engineering Ce-based promoters into active entities involved in the heterostructure to modulate intermediate adsorption, offers a great opportunity for the design of superior electrocatalysts for energy conversion.