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.

High-Strain-Induced Local Modification of the Electronic Properties of VO2 Thin Films.

Vanadium dioxide (VO2) is a popular candidate for electronic and optical switching applications due to its well-known semiconductor-metal transition. Its study is notoriously challenging due to the interplay of long- and short-range elastic distortions, as well as the symmetry change and the electronic structure changes. The inherent coupling of lattice and electronic degrees of freedom opens the avenue toward mechanical actuation of single domains. In this work, we show that we can manipulate and monitor the reversible semiconductor-to-metal transition of VO2 while applying a controlled amount of mechanical pressure by a nanosized metallic probe using an atomic force microscope. At a critical pressure, we can reversibly actuate the phase transition with a large modulation of the conductivity. Direct tunneling through the VO2-metal contact is observed as the main charge carrier injection mechanism before and after the phase transition of VO2. The tunneling barrier is formed by a very thin but persistently insulating surface layer of the VO2. The necessary pressure to induce the transition decreases with temperature. In addition, we measured the phase coexistence line in a hitherto unexplored regime. Our study provides valuable information on pressure-induced electronic modifications of the VO2 properties, as well as on nanoscale metal-oxide contacts, which can help in the future design of oxide electronics.

Morphology-tunable tellurium nanomaterials produced by the tellurite-reducing bacterium Lysinibacillus sp. ZYM-1.

Although tellurite is highly toxic to organisms, elemental tellurium nanomaterials (TeNMs) have many uses. The microbe-mediated reduction of tellurite to Te(0) has been shown to be a green and cost-effective approach for turning waste into wealth. However, it is difficult to tune the morphology of biogenic nanomaterials. In this study, a series of experiments was conducted to investigate the factors influencing tellurite reduction by the tellurite-reducing bacterium Lysinibacillus sp. ZYM-1, including pH, tellurite concentration, temperature, and heavy metal ions. The optimal removal efficiency of tellurite was respectively achieved at pH 8, 0.5 mM tellurite, and 40 °C. All of the tested metal ions retarded the reduction of tellurite, especially Cd2+ and Co2+, which completely inhibited its reduction. Further characterization of the biogenic TeNMs indicated that their morphology could be tuned by the tellurite concentration, pH, temperature, and organic solvents used. Regular Te nanosheets were produced using 5 mM tellurite. The TeNMs were primarily synthesized in the cell membrane. Hexagonal Te nanoplates, nanorods, nanoflowers, and nanobranches were synthesized when combining membrane fractions with tellurite and NADH. The diverse morphologies are assumed to be induced by the synergy between the reduction kinetics and the protein structure. Therefore, this study confirmed that the bacterium can tune the morphology of TeNMs, broadening the potential application of biogenic TeNMs.