Photophysical Study of Electron and Hole Trapping in TiO₂ and TiO₂/Au Nanoparticles through a Selective Electron Injection

The photophysics surrounding the electron and hole trapping in TiO2 do not have a scientific consensus. Herein, we studied the steady-state photoluminescence and time-resolved spectroscopy features from TiO2 and TiO2/Au nanoparticles (NPs). In TiO2/Au NPs, time-resolved photoluminescence indicates that the electrons from bandgap excitation decay slower (∼30 ps) than in TiO2 (<24 ps). We conclude this as a result of the band bending passivation effect on the surface electron traps. Meanwhile, electron trapping is proved as the dominant surface depopulation process because of the easy-fill characteristics of surface hole traps even under low excitation density, which also interprets the slow surface hole trapping (∼2 ns) in TiO2. Through plasmon-assisted electron injection, we distinguished the electron and hole behaviors at varied photon fluences and then obtained the intrinsic bulk trapping of electrons and holes in the ∼50 and ∼400 ps time range, respectively

Organic Thiol Modified Pt/TiO₂ Catalysts to Control Chemoselective Hydrogenation of Substituted Nitroarenes

The quest for selective heterogeneous hydrogenation catalysts is state of the art research. We present a simple surface modification method for Pt/TiO₂ catalysts employing organic thiols for the liquid phase selective hydrogenation of 4-nitrostyrene. Our modified catalyst shows a 100% switch of selectivity to 4-aminostyrene at conversion levels close to 100%

Real Time Determination of the Electronic Structure of Unstable Reaction Intermediates during Au₂O₃ Reduction

Chemical reactions are always associated with electronic structure changes of the involved chemical species. Determining the electronic configuration of an atom allows probing its chemical state and gives understanding of the reaction pathways. However, often the reactions are too complex and too fast to be measured at in situ conditions due to slow and/or insensitive experimental techniques. A short-lived Au₂O compound has been detected for the first time under in situ conditions during the temperature-programmed reduction of Au₂O₃. A time-resolved resonant inelastic X-ray scattering experiment (RIXS) allowed the determination of changes in the Au electronic structure, enabling a better understanding of the reaction mechanism of Au­(III) reduction. On the basis of time-resolved RIXS data analysis combined with genetic algorithm methodology, we determined the electronic structure of the metastable Au₂O intermediate species. The data analysis showed a notably larger value for the lattice constant of the intermediate Au as compared to the theoretical predictions. With support of DFT calculations, we found that such a structure may indeed be formed and that the expanded lattice constant is due to the termination of Au₂O on the Au₂O₃ structure

Redispersion of Gold Supported on Oxides

Although many gold heterogeneous catalysts have been shown to exhibit significant activity and high selectivity for a wide range of reactions in both the liquid and gas phases, they are prone to irreversible deactivation. This is often associated with sintering or loss of the interaction of the gold with the support. Herein, we report on the use of methyl iodide as a method of dispersing gold nanoparticles supported on silica, titania, and alumina supports. In the case of titania- and alumina-based catalysts, the gold was transformed from nanometer particles into small clusters and some atomically dispersed gold. In contrast, although there was a drop in the gold particle size on the silica support following CH₃I treatment, the size remained in the submicrometer range. The structural changes were correlated with changes in the selectivity and activity for ethanol dehydration and benzyl alcohol oxidation. From these observations, it is clear that this treatment provides a method by which deactivated gold catalysts can be reactivated via redispersion of the gold

Direct Determination of Metal Complexes’ Interaction with DNA by Atomic Telemetry and Multiscale Molecular Dynamics

The lack of molecular mechanistic understanding of the interaction between metal complexes and biomolecules hampers their potential medical use. Herein we present a robust procedure combining resonant X-ray emission spectroscopy and multiscale molecular dynamics simulations, which allows for straightforward elucidation of the precise interaction mechanism at the atomic level. The report unveils an unforeseen hydrolysis process and DNA binding of [Pt­{N­(p-HC₆F₄)­CH₂}₂py₂] (Pt103), which showed potential cytotoxic activity in the past. Pt103 preferentially coordinates to adjacent adenine sites, instead of guanine sites as in cisplatin, because of its hydrogen bond ability. Comparison with previous research on cisplatin suggests that selective binding to guanine or adenine may be achieved by controlling the acidity of the compound