Function of Doping Ru Element in the Hydrogen Evolution Reaction in Rare-Earth Transition-Metal Intermetallics

Transition metal-based intermetallics are promising electrocatalysts for replacing the commercial Pt metal in the hydrogen evolution reaction (HER). In this work, RENi₂ and RERu_0.25Ni_1.75 (RE = Pr, Tb, and Er) were synthesized and their electrocatalytic HER activities were explored. Among undoped compounds, PrNi₂ exhibits the best performance and requires an overpotential of 55 mV, while partially replacing Ni with Ru element (PrRu_0.25Ni_1.75) can greatly reduce the overpotential to 20 mV at a current density of 10 mA/cm². Such enhancement was recognized that belongs to their extrinsic property, and their intrinsic HER activities were similar after normalizing the electrocatalytic surface area. Further investigation on ScM₂ and ScRu_0.25M_1.75 (M = Co and Ni) suggests that doping Ru element in ScCo₂ will significantly enhance antibonding character around the Fermi level (E_F) and weaken hydrogen adsorption energy. On the other hand, the antibonding population for ScNi₂ and ScRu_0.25Ni_1.75 is similar at E_F, which accounts for their close intrinsic HER activities.