Molten-Salt-Mediated Synthesis of an Atomic Nickel Co-catalyst on TiO2 for Improved Photocatalytic H2 Evolution

Atomic co-catalysts offer high potential to improve the photocatalytic performance, of which the preparation with earth-abundant elements is challenging. Here, a new molten salt method (MSM) is designed to prepare atomic Ni co-catalyst on widely studied TiO₂ nanoparticles. The liquid environment and space confinement effect of the molten salt leads to atomic dispersion of Ni ions on TiO₂, while the strong polarizing force provided by the molten salt promotes formation of strong Ni−O bonds. Interestingly, Ni atoms are found to facilitate the formation of oxygen vacancies (OV) on TiO₂ during the MSM process, which benefits the charge transfer and hydrogen evolution reaction. The synergy of atomic Ni co-catalyst and OV results in 4-time increase in H₂ evolution rate compared to that of the Ni co-catalyst on TiO₂ prepared by an impregnation method. This work provides a new strategy of controlling atomic co-catalyst together with defects for efficient photocatalytic water splitting.     

Activation of Water-Splitting Photocatalysts by Loading with Ultrafine Rh–Cr Mixed-Oxide Cocatalyst Nanoparticles

The activity of many water-splitting photocatalysts could be improved by the use of Rh^III–Cr^III mixed oxide (Rh_2−xCr_xO₃) particles as cocatalysts. Although further improvement of water-splitting activity could be achieved if the size of the Rh_2−xCr_xO₃ particles was decreased further, it is difficult to load ultrafine (<2 nm) Rh_2−xCr_xO₃ particles onto a photocatalyst by using conventional loading methods. In this study, a new loading method was successfully established and was used to load Rh_2−xCr_xO₃ particles with a size of approximately 1.3 nm and a narrow size distribution onto a BaLa₄Ti₄O₁₅ photocatalyst. The obtained photocatalyst exhibited an apparent quantum yield of 16 %, which is the highest achieved for BaLa₄Ti₄O₁₅ to date. Thus, the developed loading technique of Rh_2−xCr_xO₃ particles is extremely effective at improving the activity of the water-splitting photocatalyst BaLa₄Ti₄O₁₅. This method is expected to be extended to other advanced water-splitting photocatalysts to achieve higher quantum yields.     

Porous TiO2 Nanotubes with Spatially Separated Platinum and CoOx Cocatalysts Produced by Atomic Layer Deposition for Photocatalytic Hydrogen Production

Efficient separation of photogenerated electrons and holes, and associated surface reactions, is a crucial aspect of efficient semiconductor photocatalytic systems employed for photocatalytic hydrogen production. A new CoO_x/TiO₂/Pt photocatalyst produced by template‐assisted atomic layer deposition is reported for photocatalytic hydrogen production on Pt and CoO_x dual cocatalysts. Pt nanoclusters acting as electron collectors and active sites for the reduction reaction are deposited on the inner surface of porous TiO₂ nanotubes, while CoO_x nanoclusters acting as hole collectors and active sites for oxidation reaction are deposited on the outer surface of porous TiO₂ nanotubes. A CoO_x/TiO₂/Pt photocatalyst, comprising ultra‐low concentrations of noble Pt (0.046 wt %) and CoO_x (0.019 wt %) deposited simultaneously with one atomic layer deposition cycle, achieves remarkably high photocatalytic efficiency (275.9 μmol h⁻¹), which is nearly five times as high as that of pristine TiO₂ nanotubes (56.5 μmol h⁻¹). The highly dispersed Pt and CoO_x nanoclusters, porous structure of TiO₂ nanotubes with large specific surface area, and the synergetic effect of the spatially separated Pt and CoO_x dual cocatalysts contribute to the excellent photocatalytic activity.