Electronic Modulation of Pt Nanoparticles Induced by Defective TiN Promotes Highly Efficient Hydrogen Evolution

ABSTRACT Regulating the microenvironment of the support enables precise control of electronic metal–support interactions (EMSI), boosting better catalytic activity of the metal species. However, the fundamental relationship between support defect‐induced EMSI modulation and the resulting catalytic performance enhancement still needs further elucidation. Herein, a nonequilibrium high‐temperature shock (HTS) method, which combines rapid high‐temperature heating at 1273 K for 30 s with liquid nitrogen quenching, was adopted to load uniform Pt nanoparticles onto the nitrogen vacancy‐rich TiN support (Pt@TiN‐V _N ). The catalyst demonstrates a high mass activity of 15.99 A mg _Pt ⁻¹ at an overpotential of 100 mV for the hydrogen evolution reaction (HER) in acidic solution and exhibits long‐term stability for 60 h at 200 mA cm ⁻² . Detailed spectroscopic characterizations and theoretical calculations reveal that the generated nitrogen vacancies can effectively modulate the charge transfer between Pt nanoparticles and the TiN‐V _N support, leading to a downshifted d‐band center of metallic Pt and optimized Pt–H bond strength. This nonequilibrium HTS approach offers new and valuable insights into designing advanced electrocatalysts by harnessing substrate defects to modulate the electronic states of loaded noble metals.