Enhanced Stability and Emission Properties of Perylene Dyes by Surface Tethering: Preparation of Fluorescent Ru Nanoparticle Suspensions by Alkyne Linker Chemistry.

Spherical ruthenium nanoparticles (NPs) with a narrow size distribution were synthesised in ethanol by a facile low-temperature solvothermal process without the assistance of templates, structure-directing agents or post annealing/reduction treatments. Surface passivation with a fluorescent perylene dye (EP), and with silane ligands (ETMS), both initially bearing alkyne groups and subsequently forming vinylidene linkages, provided stable suspensions of the marginally soluble free EP. Quantitative analysis of the suspension gave an estimated EP surface coverage of 15 %, corresponding to an EP/ETMS mole ratio of ≈1:6. Photophysical evaluation of the bound and free dye revealed similar absorption bands and extinction coefficients and improved properties for the bound state, including enhanced fluorescence in the visible range for the bound dye, an extended absorption range into the near-UV providing strong emission in the visible, and significantly improved photostability. The physical basis of the enhanced photophysical properties, potential routes to further improvements and the implications for applications are discussed.

Ti-Doped SBA-15 Catalysts Used in Phenol Oxidation Reactions.

Two Ti-SBA-15 catalysts are synthesized using techniques that should either deposit Ti atoms specifically at the SBA-15 surface or allow Ti-containing species to exist at both the surface and within the bulk of SBA-15. The materials have been characterized by Fourier transform infrared (FTIR), Raman and UV visible spectroscopies, transmission electron microscopy, scanning electron microscopy/energy-dispersive X-ray spectrometry microscopies, and N2 physisorption experiments. They have been applied in the total oxidation of phenol under catalytic wet air oxidation (CWAO) conditions and using photo- and plasma promotion. The materials retain the structure of SBA-15 following the doping in both cases and Ti incorporation is confirmed. The nature of the incorporated Ti remains unclear-with evidence for anatase TiO2 (from Raman and UV vis analysis) and evidence for atomically dispersed Ti from FTIR. In terms of reactivity, the presence of Ti in the in situ-prepared catalyst improves reactivity in the photopromoted reaction (increasing conversion from 28 to 60%), while both Ti catalysts improve reactivity in the CWAO reaction (by 7% over the in situ catalyst and by 25% over the grafted material). The presence of Ti has no beneficial effect on conversion in the plasma-promoted reaction. Here, however, Ti does affect the nature of the oxidized intermediates formed during the total phenol oxidation.