Highly Active and Stable Metal Single-Atom Catalysts Achieved by Strong Electronic Metal-Support Interactions.

ABSTRACT

Developing an active and stable metal single-atom catalyst (SAC) is challenging due to the high surface free energy of metal atoms. In this work, we report that tailoring of the 5d state of Pt1 single atoms on Co3O4 through strong electronic metal-support interactions (EMSIs) boosts the activity up to 68-fold higher than those on other supports in dehydrogenation of ammonia borane for room-temperature hydrogen generation. More importantly, this catalyst also exhibits excellent stability against sintering and leaching, in sharp contrast to the rapid deactivation observed on other Pt single-atom and nanoparticle catalysts. Detailed spectroscopic characterization and theoretical calculations revealed that the EMSI tailors the unoccupied 5d state of Pt1 single atoms, which modulates the adsorption of ammonia borane and facilities hydrogen desorption, thus leading to the high activity. Such extraordinary electronic promotion was further demonstrated on Pd1/Co3O4 and in hydrogenation reactions, providing a new promising way to design advanced SACs with high activity and stability.