TiO₂ Nanowire-Supported Sulfide Hybrid Photocatalysts for Durable Solar Hydrogen Production

As the feet of clay, photocorrosion induced by hole accumulation has placed serious limitations on the widespread deployment of sulfide nanostructures for photoelectrochemical (PEC) water splitting. Developing sufficiently stable electrodes to construct durable PEC systems is therefore the key to the realization of solar hydrogen production. Here, an innovative charge-transfer manipulation concept based on the aligned hole transport across the interface has been realized to enhance the photostability of In2S3 electrodes toward PEC solar hydrogen production. The concept was realized by conducting compact deposition of In2S3 nanocrystals on the TiO2 nanowire array. Under PEC operation, the supporting TiO2 nanowires functioned as an anisotropic charge-transfer backbone to arouse aligned charge transport across the TiO2–In2S3 interface. Because of the aligned hole transport, the TiO2 nanowire-supported In2S3 hybrid nanostructures (TiO2–In2S3) exhibited improved hole-transfer dynamics at the TiO2–In2S3 interface and enhanced hole injection kinetics at the electrode surface, substantially increasing the long-term photostability toward solar hydrogen production. The PEC durability tests showed that TiO2–In2S3 electrodes can achieve nearly 90.9% retention of initial photocurrent upon continuous irradiation for 6 h, whereas the pure In2S3 merely retained 20.8% of initial photocurrent. This double-gain charge-transfer manipulation concept is expected to convey a viable approach to the intelligent design of highly efficient and sufficiently stable sulfide photocatalysts for sustainable solar fuel generation.