Novel Dyadic Amorphous-Crystalline Nano-Titania Hybrids for Sacrifiers-Stored Photocatalysis.

Abstract Sacrifiers-promoted photocatalysis is a useful way to achieve high efficiency photoreduction and photocatalytic hydrogen production for photocatalysts of weak reductive power such as TiO2. Herein we report a new method to fabricate a unique dyadic hybrid consisting of closely compacted crystalline (anatase) and titanium glycerolate (TiG)-derived organic group-retained amorphous nanoparticles to validate adsorption-stored sacrifiers-promoted photocatalysis instead of using sacrifiers in bulk solution. It was found that ascorbic acid (AA)-modified TiG prepared at a small fraction of glycerol, characterized by peculiar cocoon/open nanocontainer-type morphologies, varieties of oxygen containing groups, and remarkably high specific surface area, is suitable for precursing such hybrids. AA can change crystallization processes and particle morphologies by terminating chain linkages in TiG structure, which increases porosity and brings about visible light responsive photocatalysis for the dyadic hybrid. Benefiting from good adsorption affinity to organic sacrifiers, the sacrifier-prestored hybrid can catalyze significantly enhanced photoreduction with good reproducibility toward dye molecules via the synergy of sacrifier enrichment and photocatalysis. AA modified TiG also exhibits good self-reducibility enabling pre-loading of highly dispersed and localized platinum nanoparticles, and the resulted dyadic hybrid facilitates photocatalytic hydrogen production of extremely higher turn-off frequency and better impurities interference-resistivity compared to the P25-based commercial catalyst.