Activating TiO2 through the Phase Transition‐Mediated Hydrogen Spillover to Outperform Pt for Electrocatalytic pH‐Universal Hydrogen Evolution

Abstract Endowing conventional materials with specific functions that are hardly available is invariably of significant importance but greatly challenging. TiO 2 is proven to be highly active for the photocatalytic hydrogen evolution while intrinsically inert for electrocatalytic hydrogen evolution reaction (HER) due to its poor electrical conductivity and unfavorable hydrogen adsorption/desorption behavior. Herein, the first activation of inert TiO 2 for electrocatalytic HER is demonstrated by synergistically modulating the positions of d‐band center and triggering hydrogen spillover through the dual doping‐induced partial phase transition. The N, F co‐doping‐induced partial phase transition from anatase to rutile phase in TiO 2 (AR‐TiO 2 |(N,F)) exhibits extraordinary HER performance with overpotentials of 74, 80, and 142 mV at a current density of 10 mA cm –2 in 1.0 M KOH, 0.5 M H 2 SO 4 , and 1.0 M phosphate‐buffered saline electrolytes, respectively, which are substantially better than pure TiO 2 , and even superior to the benchmark Pt/C catalysts. These findings may open a new avenue for the development of low‐cost alternative to noble metal catalysts for electrocatalytic hydrogen production.