Activating TiO₂ through the Phase Transition-Mediated Hydrogen Spillover to Outperform Pt for Electrocatalytic...

Endowing conventional materials with specific functions that are hardly available is invariably of significant importance but greatly challenging. TiO₂ 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 TiO₂ 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 TiO₂ (AR-TiO₂|(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 H₂SO₄, and 1.0 M phosphate-buffered saline electrolytes, respectively, which are substantially better than pure TiO₂, 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.