Electron Donor-Specific Surface Interactions Promote the Photocatalytic Activity of Metal-Semiconductor Nanohybrids

In the past two decades, the application of colloidal semiconductor-metal nanoparticles (NPs) as photocatalysts for the hydrogen generation from water has been extensively studied. The present body of literature studies agrees that the photocatalytic yield strongly depends on the electron donating agent (EDA) added for scavenging the photogenerated holes. The highest reported hydrogen production rates are obtained in the presence of ionic EDAs and at high pH. The large hydrogen production rates are attributed to fast hole transfer from the NP onto the EDAs. However, the present discussions do not treat the influence of EDA-specific surface interactions. This systematic study focuses on that aspect by combining steady-state hydrogen production measurements with time-resolved and static optical spectroscopy, employing 11-mercaptoundecanoic acid-capped, Pt-tipped CdSe/CdS dot-in-rods in the presence of a large set of EDAs. Based on the experimental results, two distinct EDA groups are identified: surface-active and diffusion-limited EDAs. The largest photocatalytic efficiencies are obtained in the presence of surface-active EDAs that induce an agglomeration of the NPs. This demonstrates that the introduction of surface-active EDAs can significantly enhance the photocatalytic activity of the NPs, despite reducing their colloidal stability and inducing the formation of NP networks. The photocatalytic activity of nanocatalysts strongly depends on the electron donating agent (EDA) introduced. In this systematic study, these differences in activity are correlated with EDA-specific surface interactions. The two groups of diffusion-limited and surface-active EDAs are identified. While the former EDAs scavenge the holes from the oxidized thiol ligand, the latter scavenge the holes directly at the nanoparticle's surface. image