Effect of Ultra-Small Platinum Single-Atom Additives on Photocatalytic Activity of the CuO_x-Dark TiO₂ System in HER

Improving the efficiency of photocatalysts for hydrogen production while minimizing the amount of noble metals used is a pressing issue in modern green energy. This study examines the effect of ultra-small Pt additives on increasing the efficiency of the CuO_x-dark TiO₂ photocatalyst used in the hydrogen evolution reaction (HER). Initially, Pt was photoreduced from the hydroxonitrate complex (Me₄N)₂[Pt₂(OH)₂(NO₃)₈] onto the surface of nanodispersed CuO_x powder obtained by pulsed laser ablation. Then, the obtained Pt-CuO_x particles were dispersed on the surface of highly defective dark TiO₂, so that the mass content of Pt in the samples varied in the range from 1.25 × 10^-5 to 10^-4. The prepared samples were examined using HRTEM, XRD, XPS, and UV-Vis DRS methods. It has been established that in the Pt-CuO_x particles, platinum is mainly present in the form of single atoms (SAs), both as Pt²⁺ (predominantly) and Pt⁴⁺ species, which should facilitate electron transfer and contribute to the manifestation of the strong metal-support interaction (SMSI) effect between SA Ptⁿ⁺ and CuO_x. In turn, in the Pt-CuO_x-dark TiO₂ samples, surface defects (O_v) and surface OH groups on dark TiO₂ particles act as "anchors", promoting the spontaneous dispersion of CuO_x in the form of sub-nanometer clusters with the reduction of Cu²⁺ to Cu¹⁺ when localized near such O_v defects. During photocatalytic HER in aqueous glycerol solutions, irradiation was found to initiate a large number of catalytically active Pt⁰-CuO_x-O_v-dark TiO₂ centers, where the SMSI effect causes electron transfer from titania to SA Pt, thus promoting better separation of photogenerated charges. As a result, ultra-small additives of Pt led to up to a 1.34-fold increase in the amount of released hydrogen, while the maximum apparent quantum yield (AQY) reached 65%.