TiO₂-based photocatalysts from type-II to S-scheme heterojunction and their applications

Photocatalysis is a promising sustainable technology to remove organic pollution and convert solar energy into chemical energy. Titanium dioxide has drawn extensive attention in this field owing to its high activity under UV light, good chemical stability, large availability, low price and low toxicity. However, the poor quantum efficiency derived from fast electron/hole recombination, the limited utilization of sunlight, and a weak reducing ability still hinder its practical application. Among the modification strategies of TiO₂ to enhance its performance, the construction of heterojunctions with other semiconductors is a powerful and versatile way to maximise the separation of photogenerated charge carriers and steer their transport toward enhanced efficiency and selectivity. Here, the research progress and current status of TiO₂ modification are reviewed, focusing on heterojunctions. A rapid evolution of the understanding of the different charge transfer mechanisms is witnessed from traditional type II to the recently conceptualised S-scheme. Particular attention is paid to different synthetic approaches and interface engineering methods designed to improve and control the interfacial charge transfer, and several cases of TiO₂ heterostructures with metal oxides, metal sulfides and carbon nitride are discussed. The application hotspots of TiO₂-based photocatalysts are summarized, including hydrogen generation by water splitting, solar fuel production by CO₂ conversion, and the degradation of organic water pollutants. Hints about less studied and emerging processes are also provided. Finally, the main issues and challenges related to the sustainability and scalability of photocatalytic technologies in view of their commercialization are highlighted, outlining future directions of development.