Bifunctional photocatalyst with tailored interface scale for cooperative glycerol selective oxidation and H2 evolution.

We propose to fabricate a bifunctional photocatalyst for cooperative glycerol selective oxidation and H2 evolution. The key role of interface scale (nanometer, subnanometer, or atomic level) on tuning catalysis performance was revealed. Specifically, series Pt/defective TiO2 with tailored interface scale were constructed by loading Pt nanoparticle, cluster, and single atom on VTi‐enriched TiO2. It was uncovered that reducing interface scale could largely improve the visible‐light utilization efficiency, the photoexcited electron–hole separation, and well tuned the band structure. It could also enhance the metal–support interaction and thus adjust the chemical behavior toward reactant molecules. The optimized isolated Pt/defective TiO2 with atomic‐level interface achieved 90.6% glycerol conversion and 87.2% C3 products selectivity, accompanied by 7250.4 μmol g−1 H2 accumulative yield. It also exhibited long‐term stability of 36 h without performance loss. Besides, the dominate active site was identified and the possible reaction mechanism was illustrated combined with Density Functional Theory (DFT) calculation and quasi in situ experiments. [ABSTRACT FROM AUTHOR]