Hydrogen evolution reaction activity related to the facet-dependent electrocatalytic performance of NiCoP from first principles

Transition metal phosphides (TMPs) have been proven to act as highly active catalysts for the hydrogen evolution reaction (HER). Recently, single-phase ternary NiCoP electrocatalysts have been shown through experiments to display remarkable catalytic activity for the HER during water splitting. But, the inherent mechanism is not well understood. Herein, the HER activity of NiCoP with low-Miller-index facets, including (111), (100), (001)-NiP-t, and (001)-CoP-t, was systematically investigated using periodic density functional theory (DFT). The calculated Gibbs free energy of hydrogen adsorption (G(H)) values reveal that all calculated facets have good catalytic activity for the HER. The (111) facet with the lowest surface energy in a vacuum has optimal G(H) values close-to-zero for a range of hydrogen coverage. Ab initio thermodynamic analysis of hydrogen coverage was conducted to obtain the stabilities of surfaces, which follow the trend: (111) > (001)-CoP-t > (100) > (001)-NiP-t at 1 atm H-2 and 298 K. We hope that this work can shed new light on further understanding the HER in relation to NiCoP and can give guidance for the design and synthesis of transition bimetal phosphide-based catalysts.