Chemical Pressure-Driven Enhancement of the Hydrogen Evolving Activity of NiP from Nonmetal Surface Doping Interpreted via Machine Learning.

The activity of NiP catalysts for the hydrogen evolution reaction (HER) is currently limited by strong H adsorption at the Ni-hollow site. We investigate the effect of surface nonmetal doping on the HER activity of the NiP termination of NiP(0001), which is stable at modest electrochemical conditions. Using density functional theory (DFT) calculations, we find that both 2 p nonmetals and heavier chalcogens provide nearly thermoneutral H adsorption at moderate surface doping concentrations. We also find, however, that only chalcogen substitution for surface P is exergonic. For intermediate surface concentrations of S, the free energy of H adsorption at the Ni-hollow site is -0.11 eV, which is significantly more thermoneutral than the undoped surface (-0.45 eV). We use the regularized random forest machine learning algorithm to discover the relative importance of structure and charge descriptors, extracted from the DFT calculations, in determining the HER activity of NiP(0001) under different doping concentrations. We discover that the Ni-Ni bond length is the most important descriptor of HER activity, which suggests that the nonmetal dopants induce a chemical pressure-like effect on the Ni-hollow site, changing its reactivity through compression and expansion.