Extending aromatic acids on TiO2 for cooperative photocatalysis with triethylamine: Violet light-induced selective aerobic oxidation of sulfides

Abstract

Designing visible light photocatalysts with a metal oxide semiconductor as the starting material could expand a new horizon for the conversion and storage of solar energy. Here, the benchmark photocatalyst TiO2 was used to pursue this goal by anchoring aromatic acids. Extending the aromatic acid was strategically deployed to design TiO2 complexes with violet light-induced selective aerobic oxidation of sulfide as the probe reaction. With benzoic acid (BA) as the initial molecule, horizontally extending one or two benzene rings furnishes 2-naphthoic acid (2-NA) and 2-anthracene acid (2-AA). Moreover, triethylamine (TEA), an electron transfer mediator, was introduced to maintain the integrity of the anchored aromatic acids. Notably, there was a direct correlation between the π-conjugation of aromatic acid ligand and the selective aerobic oxidation of sulfides. Among the three aromatic acids, 2-AA delivered the best result over TiO2 due to the most extensive π-conjugated system. Ultimately, violet light-induced selective aerobic oxidation of sulfides into corresponding sulfoxides was conveniently realized by cooperative photocatalysis of 2-AA-TiO2 with 10 mol% of TEA. This work affords an extending strategy for designing the next-generation ligands for semiconductors to expand visible light-induced selective reactions.