Pt Single Atoms Supported on Defect Ceria as an Active and Stable Dual-Site Catalyst for Alkaline Hydrogen Evolution.

Abstract

This work evaluates the feasibility of alkaline hydrogen evolution reaction (HER) using Pt single-atoms (1.0 wt %) on defect-rich ceria (Pt₁/CeO_<i>x</i>) as an active and stable dual-site catalyst. The catalyst displayed a low overpotential and a small Tafel slope in an alkaline medium. Moreover, Pt₁/CeO_<i>x</i> presented a high mass activity and excellent durability, competing with those of the commercial Pt/C (20 wt %). In this picture, the defective CeO_<i>x</i> is active for water adsorption and dissociation to create H* intermediates, providing the first site where the reaction occurs. The H* intermediate species then migrate to adsorb and react on the Pt²⁺ isolated atoms, the site where H₂ is formed and released. DFT calculations were also performed to obtain mechanistic insight on the Pt₁/CeO_<i>x</i> catalyst for the HER. The results indicate a new possibility to improve the state-of-the-art alkaline HER catalysts via a combined effect of the O vacancies on the ceria support and Pt²⁺ single atoms.