Black TiO₂ nanomaterials have recently emerged as promising candidate for efficient solar-driven photocatalytic hydrogen production. Despite the great efforts to synthesize highly reduced TiO₂, it is apparent that intermediate degree of reduction (namely grey titania) brings about the formation of unique defective catalytic sites enabling co-catalyst free hydrogen generation. A precise understanding on the structural and electronic nature of this catalytically active site is still elusive, as well as the fundamental structure-activity relationships that govern formation of crystal defects, increased light absorption, charge separation and photocatalytic activity. In this perspective we discuss basic concepts that underlies an effective design of reduced TiO₂ photocatalysts for hydrogen production such as (i) defects formation in reduced TiO₂, (ii) analysis of structure deformation and presence of unpaired electrons through electron paramagnetic resonance spectroscopy, (iii) insights from surface science on electronic singularities due to defects, and (iv) photocatalysis with reduced TiO₂ classified as Pt-modified and co-catalyst-free photocatalytic hydrogen generation. Finally, future directions to improve the performance of reduced TiO₂ photocatalysts are outlined.

Single‐atom (SA) catalysis is a novel frontline in the catalysis field due to the often drastically enhanced specific activity and selectivity of many catalytic reactions. Here, an atomic‐scale defect engineering approach to form and control traps for platinum SA sites as co‐catalyst for photocatalytic H₂ generation is described. Thin sputtered TiO₂ layers are used as a model photocatalyst, and compared to the more frequently used (001) anatase sheets. To form stable SA platinum, the TiO₂ layers are reduced in Ar/H₂ under different conditions (leading to different but defined Ti³⁺‐O_v surface defects), followed by immersion in a dilute hexachloroplatinic acid solution. HAADF‐STEM results show that only on the thin‐film substrate can the density of SA sites be successfully controlled by the degree of reduction by annealing. An optimized SA‐Pt decoration can enhance the normalized photocatalytic activity of a TiO₂ sputtered sample by 150 times in comparison to a conventional platinum‐nanoparticle‐decorated TiO₂ surface. HAADF‐STEM, XPS, and EPR investigation jointly confirm the atomic nature of the decorated Pt on TiO₂. Importantly, the density of the relevant surface exposed defect centers—thus the density of Pt‐SA sites, which play the key role in photocatalytic activity—can be precisely optimized.