Despite the promising performance of Ru nanoparticles or nanoclusters on nanostructured TiO₂ in photocatalytic and photothermal reactions, a mechanistic understanding of the photophysics is limited. The aim of this study is to uncover the nature of light-induced processes in Ru/TiO₂ and the role of UV versus visible excitation by time-resolved photoluminescence (PL) spectroscopy. The PL at a 267 nm excitation is predominantly due to TiO₂, with a minor contribution of the Ru nanoclusters. Relative to TiO₂, the PL of Ru/TiO₂ following a 267 nm excitation is significantly blue-shifted, and the bathochromic shift with time is smaller. We show by global analysis of the spectrotemporal PL behavior that for both TiO₂ and Ru/TiO₂ the bathochromic shift with time is likely caused by the diffusion of electrons from the TiO₂ bulk toward the surface. During this directional motion, electrons may recombine (non)radiatively with relatively immobile hole polarons, causing the PL spectrum to red-shift with time following excitation. The blue-shifted PL spectra and smaller bathochromic shift with time for Ru/TiO₂ relative to TiO₂ indicate surface PL quenching, likely due to charge transfer from the TiO₂ surface into the Ru nanoclusters. When deposited on SiO₂ and excited at 532 nm, Ru shows a strong emission. The PL of Ru when deposited on TiO₂ is completely quenched, demonstrating interfacial charge separation following photoexcitation of the Ru nanoclusters with a close to unity quantum yield. The nature of the charge-transfer phenomena is discussed, and the obtained insights indicate that Ru nanoclusters should be deposited on semiconducting supports to enable highly effective photo(thermal)catalysis.

The role of Pt on photocatalytic substrates such as TiO₂ (P25) for the decomposition of organic pollutants is still controversial in the scientific community. The well-observed behavior of an optimum catalytic activity as a function of the Pt loading is usually explained by the shift from charge separation to charge recombination behavior of Pt clusters. However, experiments supporting this explanation are still lacking to give a concise understanding of the effect of Pt on the photocatalytic activity. Here, we present an experimental study that tries to discriminate the different effects influencing the photocatalytic activity. Using atomic layer deposition in a fluidized bed reactor, we prepared TiO₂ (P25) samples with Pt loadings ranging from 0.04 wt % to around 3 wt %. In order to reveal the mechanism behind the photocatalytic behavior of Pt on P25, we investigated the different aspects (i.e., surface area, reactant adsorption, light absorption, charge transfer, and reaction pathway) of heterogeneous photocatalysis individually. In contrast to the often proposed prolonged lifetime of charge carriers in Pt-loaded TiO₂, we found that after collecting the excited electrons, Pt acts more as a recombination center independent of the amount of Pt deposited. Only when dissolved O₂ is present in the solution, charge recombination is suppressed by the subsequential consumption of electrons at the surface of the Pt clusters with the dissolved O₂ benefited by the improved O₂ adsorption on the Pt surface.