Engineering Vacancy-Atom Ensembles to Boost Catalytic Activity toward Hydrogen Evolution

The dissociation of water is the rate-determining step of several energy-relating reactions due to high energy barrier in homolysis of H-O bond. Herein, engineering vacancy-atom ensembles via injecting oxygen vacancy (V-O) into single facet-exposed TiO2-Pd catalyst to form V-O-Pd ensemble is proposed and implemented. The outstanding activity of as-prepared catalyst, 1.5-PdTVO, toward water dissociation is established with a turnover frequency of 240 min(-1) in ammonia borane hydrolysis at 298 K. Density functional theory simulation suggests that the V-O-Pd ensemble is responsible for the high intrinsic catalytic activity. Water molecules tend to be dissociated on V-O sites and ammonia borane molecules on Pd atoms. Those H atoms from water dissociation on V-O combine with H atoms from ammonia borane on Pd atoms to generate H-2. This insights into engineering vacancy-atom ensembles catalysis provide a new avenue to design catalytic materials for important energy chemical reactions.

Automated summary

In this study, engineering vacancy-atom ensembles were proposed and implemented by injecting oxygen vacancies (V-O) to form V-O-Pd ensembles in single facet-exposed TiO2-Pd catalysts. The as-prepared catalyst, 1.5-PdTVO, exhibited outstanding activity in water dissociation. Theoretical simulations showed that the V-O-Pd ensemble played a key role in the high catalytic activity.