Thiocoumarin-based Au(I) Complexes and Au(0) Systems over TiO2 as Hybrid Photocatalysts for Hydrogen Generation under UV-Vis Light

This work focuses on the photocatalytic production of hydrogen from the photodehydrogenation of ethanol using several gold(I) complexes and gold(0) systems over titanium dioxide (P90 TiO2) as hybrid photocatalysts. The photocatalytic systems are composed of at least one coumarin-based ligand, which can enhance the photocatalytic activity by its photon-absorbing capacity due to its chromophore properties. The photocatalytic behavior for hydrogen generation of the studied samples is compared under UV-vis light setting the total gold-based co-catalyst loading at 1 wt% onto the TiO2 photocatalysts and when the gold content is maintained at 0.25 wt%. The incorporation of gold co-catalysts results in an enhancement of hydrogen production up to 2.7 times compared to a conventional Au/TiO2 reference sample. The results show an increase in the total hydrogen production under UV-vis light due to the combined presence of coumarin chromophore, gold-based co-catalysts, and gold plasmonic nanoparticles. A deep characterization of the samples from each group is performed by UV-vis spectroscopy, XPS, HRTEM, and HAADF-STEM, observing the presence of plasmonic gold nanoparticles for sample "AuL1NPs" and the reduction of the gold present in sample "AuL1a," which explains the highest observed hydrogen production rates of this study.