Photocatalytic water splitting and organic reforming based on nano-sized composites are gaining increasing interest due to the possibility of generating hydrogen by employing solar energy with low environmental impact. Although great efforts in developing materials ensuring high specific photoactivity have been recently recorded in the literature survey, the solar-to-hydrogen energy conversion efficiencies are currently still far from meeting the minimum requirements for real solar applications. This review aims at reporting the most significant results recently collected in the field of hydrogen generation through photocatalytic water splitting and organic reforming, with specific focus on metal-based semiconductor nanomaterials (e.g., metal oxides, metal (oxy)nitrides and metal (oxy)sulfides) used as photocatalysts under UVA or visible light irradiation. Recent developments for improving the photoefficiency for hydrogen generation of most used metal-based composites are pointed out. The main synthesis and operating variables affecting photocatalytic water splitting and organic reforming over metal-based nanocomposites are critically evaluated.

Several studies have shown that combining TiO₂ and Cu₂O enhances the photocatalytic activity of the material by generating a heterojunction capable of extending the light absorption in the visible and reducing the electron-hole recombination rate. Ball milling has been chosen as an alternative methodology for photocatalyst preparation, among the several techniques documented in the literature review. The results of a previously reported investigation enabled the identification of the most effective photocatalyst that can be prepared for hydrogen generation by combining Cu₂O and TiO₂ (i.e., 1%wt. Cu₂O in TiO₂ photocatalyst prepared by ball-milling method at 200 rpm and 1 min milling time). To optimize photocatalytic hydrogen generation in the presence of the greatest photocatalyst, the effects of (i) sacrificial species and their concentration, (ii) temperature, and (iii) pH of the system are taken into account, resulting in a light-to-chemical energy efficiency of 8% under the best-tested conditions. Last but not least, the possibility of using the present photocatalytic system under direct solar light irradiation is evaluated: the results indicate that nearly 60% of the hydrogen production recorded under sunlight can be attributed to the visible component of the solar spectrum, while the remaining 40% can be attributed to the UV component.