Chemical Pressure-Driven Enhancement of the Hydrogen Evolving Activity of Ni₂P from Nonmetal Surface Doping Interpreted via Machine Learning

The activity of Ni2P catalysts for the hydrogen evolution reaction (HER) is currently limited by strong H adsorption at the Ni3-hollow site. We investigate the effect of surface nonmetal doping on the HER activity of the Ni3P2 termination of Ni2P­(0001), which is stable at modest electrochemical conditions. Using density functional theory (DFT) calculations, we find that both 2p 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 Ni3-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 Ni2P­(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 Ni3-hollow site, changing its reactivity through compression and expansion.