Microwave Phosphine‐Plasma‐Assisted Ultrafast Synthesis of Halogen‐Doped Ru/RuP2 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/RuP2) 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/RuP2 favors the water dissociation and following hydrogen adsorption/desorption process. Then, the as‐synthesized Br‐Ru/RuP2 exhibits low overpotential of 34 mV to reach 10 mA cm−2 coupled with small Tafel slope of 27 mV dec−1 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. Ultrafast microwave plasma is developed to synthesize halogen elements‐doped Ru/RuP2 (X‐Ru/RuP2). The Br‐doped electrocatalyst (Br‐Ru/RuP2) exhibits excellent catalytic performances for hydrogen evolution reaction with 34 mV in 1.0 m KOH to achieve 10 mA cm−2.