Ultrafine Co-MoC particles in porous carbon derived from polyoxometalate-based metal organic framework for efficient hydrogen evolution reaction.

Accurately regulating ultrafine molybdenum carbide (MoC)-based catalysts is a significant challenge in the rational design of hydrogen evolution reaction (HER) electrocatalysts. Herein, under the guidance of the first principle calculations, we proposed an in-situ polyoxometalate-confined strategy for creating uniformly distributed ultrafine Co-MoC bimetallic nanoparticles in porous carbon nanostars, with the assistance of precisely designed metal-organic framework (MOF). The Co-MoC@C electrocatalyst has a high specific surface area of 969 m2·g-1 because of the conductive carbon substrate with abundant mesopores, which makes for exposing more active sites of Co-MoC nanocrystals (∼1.5 nm) and facilitating electron/ion transport. Thus, Co-MoC@C electrocatalyst shows the excellent electrochemical activity with overpotentials of 88.4 mV and 66.6 mV at a current density of 10 mA·cm-2 under acidic and alkaline conditions, respectively. The in-situ polyoxometalate-confined strategy will provide a new guideline for the design and preparation of efficient HER electrocatalysts.