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Semiconductors-based heterogeneous photocatalytic water splitting has been extensively studied, but it still remains challenging to accelerate the separation of electron–hole pairs and facilitate the reaction kinetics. Here we report a general strategy to fabricate highly efficient Pt/TiO2 photocatalyst by coupling the Pt co-catalysts and surface oxygen vacancies (VO) of TiO2. TiO2 was pre-modified with alkali or alkaline earth metals ion solutions, which produce a large number of surface hydroxyl on TiO2. Subsequently, the photodeposited Pt sub-nanoparticles substitute surface hydroxyl and induce surface VO on TiO2. The coupling of Pt and surface VO on TiO2 can accelerate the extraction of photo-charges through the interaction of Pt–VO–Ti bonds and reduce the hydrogen evolution barrier, thereby promoting the photocatalytic activity. The synthesized Pt-VO-TiO2 sample exhibits a photocatalytic hydrogen evolution activity as high as 1.5 L·g−1·h−1, which is 2.2 times that of traditional Pt/TiO2. Our findings in-depth understand the synergistic effect of co-catalysts and defects on photocatalysis and open up new possibilities for achieving robust photocatalytic water splitting.
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