Photophysical Characterization of Ru Nanoclusters on Nanostructured TiO2 by Time-Resolved Photoluminescence Spectroscopy.

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.

Unraveling the Mechanisms of Beneficial Cu-Doping of NiO-Based Photocathodes.

Dye-sensitized photoelectrochemical (DSPEC) water splitting is an attractive approach to convert and store solar energy into chemical bonds. However, the solar conversion efficiency of a DSPEC cell is typically low due to a poor performance of the photocathode. Here, we demonstrate that Cu-doping improves the performance of a functionalized NiO-based photocathode significantly. Femtosecond transient absorption experiments show longer-lived photoinduced charge separation for the Cu:NiO-based photocathode relative to the undoped analogue. We present a photophysical model that distinguishes between surface and bulk charge recombination, with the first process (∼10 ps) occurring more than 1 order of magnitude faster than the latter. The longer-lived photoinduced charge separation in the Cu:NiO-based photocathode likely originates from less dominant surface recombination and an increased probability for holes to escape into the bulk and to be transported to the electrical contact of the photocathode. Cu-doping of NiO shows promise to suppress detrimental surface charge recombination and to realize more efficient photocathodes.

Hydrogen-Generating Ru/Pt Bimetallic Photocatalysts Based on Phenyl-Phenanthroline Peripheral Ligands.

Recent studies on hydrogen-generating supramolecular bimetallic photocatalysts indicate a more important role of the peripheral ligands than expected, motivating us to design a Ru/Pt complex with 4,7-diphenyl-1,10-phenanthroline peripheral ligands. Photoinduced intra- and inter-ligand internal conversion processes have been investigated using transient absorption spectroscopy, spanning the femto- to nanosecond timescale. After photoexcitation and ultrafast intersystem crossing, triplet states localised on either the peripheral ligands or on the bridging ligand/catalytic unit are populated in a non-equilibrated way. Time-resolved photoluminescence demonstrates that the lifetime for the Ru/Pt dinuclear species (795±8 ns) is significantly less than that of the mononuclear analogue (1375±20 ns). The photocatalytic studies show modest hydrogen turnover numbers, which is possibly caused by the absence of an excited state equilibrium. Finally, we identify challenges that must be overcome to further develop this class of photocatalysts and propose directions for future research.

Methods, Mechanism, and Applications of Photodeposition in Photocatalysis: A Review.

In this review, for a variety of metals and semiconductors, an attempt is made to generalize observations in the literature on the effect of process conditions applied during photodeposition on (i) particle size distributions, (ii) oxidation states of the metals obtained, and (iii) consequences for photocatalytic activities. Process parameters include presence or absence of (organic) sacrificial agents, applied pH, presence or absence of an air/inert atmosphere, metal precursor type and concentration, and temperature. Most intensively reviewed are studies concerning (i) TiO2; (ii) ZnO, focusing on Ag deposition; (iii) WO3, with a strong emphasis on the photodeposition of Pt; and (iv) CdS, again with a focus on deposition of Pt. Furthermore, a detailed overview is given of achievements in structure-directed photodeposition, which could ultimately be employed to obtain highly effective photocatalytic materials. Finally, we provide suggestions for improvements in description of the photodeposition methods applied when included in scientific papers.

Sorption-determined deposition of platinum on well-defined platelike WO3.

The photodeposition of Pt nanoparticles from [PtCl6 ](2-) on platelike WO3 crystals occurs preferentially on the small, subordinate facets. Rather than the often-used explanation of preferred light-induced charge migration, we propose that this phenomenon is due to differences in the intrinsic surface charges of WO3 facets exposed to water; thus, the dark sorption of [PtCl6 ](2-) on positively charged facets/edges is preferred. This conclusion is based on 1) (dark) impregnation studies, which showed Pt deposition to also be facet-specific, and 2) aqueous-phase AFM studies, which suggest intrinsic surface charges to be in agreement with sorption-based Pt distributions.