Single-Atom Pt Doping Induced p-Type to n-Type Transition in NiO Nanosheets toward Self-Gating Modulated Electrocatalytic Hydrogen Evolution Reaction

Exploring highly efficient single atom catalysts with defined active centers and tunable electronic structures is highly desirable. Herein, we developed an efficient hydrogen evolution reaction (HER) electrocatalyst through a self-gating phenomenon induced by Pt single atoms (SAs) supported on ultrathin NiO nanosheets (Pt_SA-NiO). The Ni atoms in NiO are partially replaced by the atomically dispersed Pt atoms, leading to a transition from p-type NiO into n-type Pt_SA-NiO. When the n-type Pt_SA-NiO serves as HER electrocatalyst, the self-gating phenomenon occurs in the ultrathin nanosheets, resulting in a mixture of leakage ("active") and metal-insulator-semiconductor ("inert") regions. The "inert" region induced by the ionic gating and reverse potential is capable of accumulating relatively high surface charge carrier concentration with an ultrahigh electric field, making the Pt_SA-NiO highly conductive; meanwhile, the HER process occurs at the Pt SAs sites (active region) in the Pt_SA-NiO nanosheets. As a result, the Pt_SA-NiO requires only 55 mV to deliver 10 mA/cm² in an alkaline solution with good stability.