Self-assembled monolayers enhance the efficiency of Pt single atom co-catalysts in photocatalytic H2 generation

•We decorate Pt single-atoms on anodic titania surfaces by a simple immersion technique.•We compare SA deposition on plain TiO2 layers, with TiO2 layers that were modified by silane self-assembled monolayer (SAM).•SAM modified TiO2 layers can generate 3 times more photocatalytic H2.•To activate the surface, the SAMs need to be cut by a chain treatment.•We provide a new perspective for single atom co-catalyzed photocatalysis. Single atom (SA) catalysis, over the last 10 years, has become a forefront in heterogeneous catalysis, electrocatalysis, and most recently also in photocatalysis. Pt SAs on titania have been reported to be a highly effective co-catalyst in photocatalytic H2 generation. Most recently, for the synthesis of SA loading on titania surfaces, some simple immersion techniques have been described. Here we introduce a so far unexplored but evidently very effective approach to enhance the effectivity of Pt SA co-catalysts on anodic TiO2 layers. For this, we first decorate TiO2 surfaces with a partial coverage of headgroups of silane self-assembled monolayers (SAMs) and then deposit Pt SAs on this SAM modified surface. We observe a significantly enhanced photocatalytic activity for H2 generation using this sensitization of the surface with a modified SAM.