Enhanced Photocatalytic Hydrogen Production Activity by Constructing a Robust Organic-Inorganic Hybrid Material Based Fulvalene and TiO₂

Abstract

A novel redox-active organic-inorganic hybrid material (denoted as H4TTFTB-TiO2) based on tetrathiafulvalene derivatives and titanium dioxide with a micro/mesoporous nanomaterial structure has been synthesized via a facile sol-gel method. In this study, tetrathiafulvalene-3,4,5,6-tetrakis(4-benzoic acid) (H4TTFTB) is an ideal electron-rich organic material and has been introduced into TiO2 for promoting photocatalytic H2 production under visible light irradiation. Notably, the optimized composites demonstrate remarkably enhanced photocatalytic H2 evolution performance with a maximum H2 evolution rate of 1452 μmol g−1 h−1, which is much higher than the prototypical counterparts, the common dye-sensitized sample (denoted as H4TTFTB-5.0/TiO2) (390.8 μmol g−1 h−1) and pure TiO2 (18.87 μmol g−1 h−1). Moreover, the composites perform with excellent stability even after being used for seven time cycles. A series of characterizations of the morphological structure, the photoelectric physics performance and the photocatalytic activity of the hybrid reveal that the donor-acceptor structural H4TTFTB and TiO2 have been combined robustly by covalent titanium ester during the synthesis process, which improves the stability of the hybrid nanomaterials, extends visible-light adsorption range and stimulates the separation of photogenerated charges. This work provides new insight for regulating precisely the structure of the fulvalene-based composite at the molecule level and enhances our in-depth fundamental understanding of the photocatalytic mechanism.

Keywords

• photocatalysis
• titanium dioxide (TiO₂)
• tetrathiafulvalene derivatives
• organic-inorganic hybrid nanomaterials
• sol-gel method