Electronic Structure Engineering of Pt Species over Pt/WO3 toward Highly Efficient Electrocatalytic Hydrogen Evolution

Abstract Pt‐based supported materials, a widely used electrocatalyst for hydrogen evolution reaction (HER), often experience unavoidable electron loss, resulting in a mismatching of electronic structure and HER behavior. Here, a Pt/WO3 catalyst consisting of Pt species strongly coupled with defective WO3 polycrystalline nanorods is rationally designed. The electronic structure engineering of Pt sites on WO3 can be systematically regulated, and so that the optimal electron‐rich Pt sites on Pt/WO3‐600 present an excellent HER activity with only 8 mV overpotential at 10 mA cm−2. Particularly, the mass activity reaches 7015 mA mg−1 at the overpotential of 50 mV, up to 26‐fold higher than that of the commercial Pt/C. The combination of experimental and theoretical results demonstrates that the O vacancies of WO3 effectively mitigate the tendency of electron transfer from Pt sites to WO3, so that the d‐band center could reach an appropriate level relative to Fermi level, endowing it with a suitable . This work identifies the influence of the electronic structure on catalytic activity.