A Combined experimental and theoretical study of the accelerated hydrogen evolution kinetics over wide pH range on porous transition metal doped tungsten phosphide electrocatalysts

Modifying the nanostructures and chemical compositions provides an opportunity of developing the effective and inexpensive hydrogen evolution reaction (HER) electrocatalysts. Herein, porous transition metal doped tungsten phosphide (M-WP, M=Mo, Co) catalysts have been developed as enhanced HER electrocatalysts in comparison with pristine WP. Owing to the incorporated transition metals, the as-prepared M-WP nanomaterials exhibit porous nanostructures, abundant active sites and reduced charge transfer resistances. Density functional theory (DFT) calculations further demonstrate that the Co dopant simultaneously facilitates the water dissociation step and optimizes the hydrogen adsorption free energy during the entire HER process. Consequently, the Co-WP catalyst shows efficient and stable HER performance over wide pH range. This work demonstrates how metal dopants promote the HER kinetics and develops the strategy for further designing non-precious metal based nanomaterials for energy conversion and electrocatalysis.