Dewetting of PtCu Nanoalloys on TiO2 Nanocavities Provides a Synergistic Photocatalytic Enhancement for Efficient H2 Evolution

We investigate the co-catalytic activity of PtCu alloy nanoparticles for photocatalytic H2 evolution from methanol-water solutions. To produce the photocatalysts, a few nm-thick Pt-Cu bilayers are deposited on anodic TiO2 nanocavity arrays and converted by solid state dewetting, i.e. a suitable thermal treatment, into bimetallic PtCu nanoparticles. XRD and XPS results prove the formation of PtCu nanoalloys that carry a shell of surface oxides. XANES data support Pt and Cu alloying and indicate the presence of lattice disorder in the PtCu nanoparticles. The PtCu co-catalyst on TiO2 shows a synergistic activity enhancement and a significantly higher activity towards photocatalytic H2 evolution than Pt- or Cu-TiO2. We propose the enhanced activity to be due to Pt-Cu electronic interactions, where Cu increases the electron density on Pt favoring a more efficient electron transfer for H2 evolution. In addition, Cu can further promote the photo-activity by providing additional surface catalytic sites for hydrogen recombination. Remarkably, when increasing the methanol concentration up to 50 vol% in the reaction phase, we observe for PtCu-TiO2 a steeper activity increase compared to Pt-TiO2. A further increase in methanol concentration (up to 80 vol%) causes for Pt-TiO2 a clear activity decay, while PtCu-TiO2 still maintains a high level of activity. This suggests an improved robustness of PtCu nanoalloys against poisoning from methanol oxidation products such as CO.