Step-scheme perylenediimide supramolecular nanosheet and TiO2 nanoparticle composites for boosted water splitting performance

Adjusting the band gap of organic-inorganic composites by chemical bonding can effectively construct Step-scheme (S-scheme) heterojunctions, featuring properties of fast photogenerated charge migration and excellent photocatalytic performance. In this work, a novel perylene-3, 4, 9, 10-tetracarboxylicdiimide (PDI)-titanium dioxide (TiO2) heterojunction is elaborately synthesized through simple solvent compounding method. The monodispersed spherical TiO2 nanoparticles was prepared with the capping agents of oleylamine and oleic acid, and suffered by a ligand exchange process with nitrosonium tetrafluoroborate (NOBF4) to remove oleylamine and oleic acid. The NOBF4 ligands were further replaced by PDI super molecular nanosheets to obtain two dimensional (2D)-zero dimensional (0D) PDI-TiO2 composites. TiO2 nanoparticles are evenly anchored on the surface of PDI nanosheets with intimate contact. The PDI-TiO2 composites has emerged considerably superior activity in hydrogen evolution. The highest hydrogen evolution rate for PDI-TiO2composites with the PDI weight percentage of 2.4% was 9766 μmol h−1 g−1 under solar light irradiation, which is 2.56 times of TiO2-NOBF4 catalyst. Moreover, PDI-TiO2 composites possess stoichiometric overall water splitting performance with H2 and O2 release rates of 238.20 and 114.18 μmol h−1 g−1. The superior photocatalytic performance of PDI-TiO2 composites can be attributed to the dramatic increase in visible and NIR light absorption caused by π-π stacking structure of PDI, the prevented charge recombination by the S-scheme heterojunction, and the enhanced oxygen evolution by the stronger oxidation capability of PDI. PDI supramolecular nanosheets may work as a novel functional support for many types of semiconductor nanomaterials as graphene, which will display a wide range of application prospects in the energy and environmental fields.