With recent advances in the field of single-atoms (SAs) used in photocatalysis, an unprecedented performance of atomically dispersed co-catalysts has been achieved. However, the stability and agglomeration of SA co-catalysts on the semiconductor surface may represent a critical issue in potential applications. Here, the photoinduced destabilization of Pt SAs on the benchmark photocatalyst, TiO2 , is described. In aqueous solutions within illumination timescales ranging from few minutes to several hours, light-induced agglomeration of Pt SAs to ensembles (dimers, multimers) and finally nanoparticles takes place. The kinetics critically depends on the presence of sacrificial hole scavengers and the used light intensity. Density-functional theory calculations attribute the light induced destabilization of the SA Pt species to binding of surface-coordinated Pt with solution-hydrogen (adsorbed H atoms), which consequently weakens the Pt SA bonding to the TiO2 surface. Despite the gradual aggregation of Pt SAs into surface clusters and their overall reduction to metallic state, which involves >90% of Pt SAs, the overall photocatalytic H2 evolution remains virtually unaffected.

Department of Chemistry Faculty of Science King Abdulaziz University P O Box 80203 Jeddah 21569 Saudi Arabia

Department of Materials Science and Engineering Chair for Surface Science and Corrosion Friedrich Alexander Universität Erlangen Nürnberg Martensstrasse 7 91058 Erlangen Germany

Department of Materials Science and Engineering School of Industrial Engineering and Management KTH Royal Institute of Technology Brinellvägen 23 Stockholm 10044 Sweden

Faculty of Physical Chemistry University of Belgrade Studentski trg 12 16 Belgrade 11000 Serbia

Institute of Catalysis Research and Technology and Institute for Chemical Technology and Polymer Chemistry Karlsruhe Institute of Technology 76131 Karlsruhe Germany

Institute of Micro and Nanostructure Research and Center for Nanoanalysis and Electron Microscopy IZNF Friedrich Alexander Universität Erlangen Nürnberg Cauerstraße 3 91058 Erlangen Germany

Regional Centre of Advanced Technologies and Materials Šlechtitelů 27 Olomouc 78371 Czech Republic

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