Microwave Phosphine-Plasma-Assisted Ultrafast Synthesis of Halogen-Doped Ru/RuP with Surface Intermediate Adsorption Modulation for Efficient Alkaline Hydrogen Evolution Reaction.

Anionic modification engineering is a crucial approach to develop highly efficient electrocatalysts for hydrogen evolution reaction. Herein, halogen elements (X = Cl, Br, and I)-modified Ru-based nanosheets (X-Ru/RuP) are designed by rapid and eco-friendly microwave-phosphide plasma approach within 60 s. Experimental and density functional theory calculations verify that the introduced halogen element, especially Br, can optimize the surface intermediates adsorption. Specially, the designed Br-Ru/RuP favors the water dissociation and following hydrogen adsorption/desorption process. Then, the as-synthesized Br-Ru/RuP exhibits low overpotential of 34 mV to reach 10 mA cm coupled with small Tafel slope of 27 mV dec in alkaline electrolyte with excellent long-term stability. Moreover, the electrocatalytic performances in acid and neutral media are also boosted via Br element modification. This work paves a novel way to regulate the electronic structure of Ru-based compounds, and then can boost the electrocatalytic kinetics.