The Fabrication of Pd Single Atoms/Clusters on COF Layers as Co-catalysts for Photocatalytic H₂ Evolution

The particle size of co-catalysts significantly affects the activity of semiconductors in photocatalysis. Herein, we report that the photocatalytic H₂ evolution (PHE) activity of a visible light responsive covalent organic framework (COF) layer supported on SiO₂ nanoparticles was greatly promoted from 47.7 to 85.5 μmol/h by decreasing the particle size of the Pd co-catalyst from 3.3 nm to single atoms/clusters. A PHE rate of 156 mmol g_COF^-1 h^-1 and apparent quantum efficiency up to 7.3% were achieved with the Pd SAs/Cs co-catalyst. The relationship between the activity of Pd in H₂ dissociation, proton reduction, and PHE rate suggests that the promotion effect of Pd SAs/Cs is mainly attributed to their enhancement in charge separation of COF layers rather than proton reduction. Furthermore, a photoactive film was fabricated and steady production of H₂ was achieved under visible light irradiation and static conditions. The optimization of the particle size of co-catalysts provides an efficient method for enhancing the photocatalytic activity of semiconductors.