Abstract

AbstractFor more than 20 years, Pt/TiO2 represents the benchmark photocatalyst/co‐catalyst platform for photocatalytic hydrogen (H2) generation. Here, single atom (SA) Pt is decorated on different polymorphs of TiO2 (anatase, rutile, and the mixed phase of P25) using a simple immersion anchoring approach. On P25 and anatase, Pt SAs act as highly effective co‐catalyst for pure water splitting with a photocatalytic H2 evolution activity (4600 µmol h−1 g−1)—on both polymorphs, SA deposition yields a significantly more active photocatalyst than those decorated with classic Pt nanoparticles or conventional SA deposition approaches. On rutile, Pt SAs provide hardly any co‐catalytic effect. Most remarkable, for P25, the loading of Pt SAs from precursor solution with a very low concentration (<1 ppm Pt) leads already to a maximized co‐catalytic effect. This optimized efficiency is obtained at 5.3 × 105 atoms µm−2 (at macroscopic loading of 0.06 at%)—for a higher concentration of Pt (a higher density of SAs), the co‐catalytic efficiency is significantly reduced due to H2/O2 recombination. The interactions of the SA Pt with the different polymorphs that lead to this high co‐catalytic activity of SA Pt at such low concentrations are further discussed.

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