Thermal Shock Induced Oxygen Vacancies-Rich TiO₂ Supported Pt Nanoparticles for Boosting Hydrogen Evolution Reaction

Abstract

The regulation of oxygen vacancies in metal oxide matrices is crucial for achieving efficient supported catalysts, albeit posing significant challenges. In this work, we propose a facile thermal shock method as an alternative to the conventional prolonged calcination process for synthesizing highly dispersed Pt nanoparticles supported on a TiO₂ substrate with abundant oxygen vacancies (referred to as Pt@O_v-TiO₂), which is achieved by utilizing a movable hot bed that shuttled between a high temperature heating zone and a liquid nitrogen cooling zone. A sudden heating-to-cooling pyrolytic conversion process spanning not only endows substrates with abundant oxygen vacancies but also yields small and well-dispersed noble metal nanoparticles. The Pt@O_v–TiO₂ catalyst demonstrates exceptional electrocatalytic hydrogen evolution reaction (HER) performance in acidic media, achieving a current density of 10 mA cm⁻² at a low potential of 39.9 mV. Furthermore, it exhibits superior mass activity and remarkable stability compared to commercial Pt/C catalysts. Density functional theory (DFT) calculations demonstrate the introduction of oxygen vacancies contributes to a stronger interaction between TiO₂ substrate and Pt, optimizing the free energy of hydrogen adsorption on the electron-rich Pt species, thereby enhancing the electrocatalytic HER performance. This finding provides a pathway for understanding the synergistic modulation of support defects and noble metal particles, thereby optimizing the interaction between the support and metal in substrate-supported metal electrocatalysts for highly efficient hydrogen production.

Keywords

hydrogen evolution reaction / oxygen vacancies / Pt nanoparticles / thermal shock method / TiO₂

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