Amine-functionalised hexagonal mesoporous silica as support for copper(II) acetylacetonate catalyst

Copper(II) acetylacetonate was anchored onto a hexagonal mesoporous silica (HMS) material using a two-step procedure: (i) functionalisation of the surface hydroxy groups with (3-aminopropyl)triethoxysilane (AMPTSi) and then (ii) anchoring of the copper(II) complex through Schiff condensation with free amine groups, using two different metal complex loadings. Upon the first step, nitrogen elemental analysis, XPS and DRIFT showed the presence of amine groups on the surface of the HMS material, and porosimetry indicated that the structure of the mesoporous material remained unchanged, although a slight decrease in surface area was observed. Atomic absorption, XPS and DRIFT showed that copper(II) acetylacetonate was anchored onto the amine-functionalised HMS by Schiff condensation between the free amine groups and the carbonyl groups of the copper(II) complex; using EPR an NO3 coordination sphere was proposed for the anchored copper(II) complex. The new [Cu(acac)2]-AMPTSi/HMS materials were tested in the aziridination of styrene at room temperature, using PhI=NTs as nitrogen source and acetonitrile as solvent. The styrene conversion and total TON of the heterogeneous phase reaction are higher than those of the same reaction catalysed in homogeneous phase by [Cu(acac)2]; nevertheless, the initial activity decreases and the reaction time increases due to substrate and product diffusion limitations. The heterogeneous catalyst showed a successive slight decrease in catalytic activity when reused for two more times. © Wiley-VCH Verlag GmbH & Co. KGaA, 2006.

UV-stable paper coated with APTES-modified P25 TiO2 nanoparticles

In order to inhibit the photocatalytic degradation of organic material supports induced by small titania (TiO2) nanoparticles, highly photocatalytically active, commercially available P25-TiO2 nanoparticles were first modified with a thin layer of (3-aminopropyl) triethoxysilane (APTES), which were then deposited and fixed onto the surface of paper samples via a simple, dip-coating process in water at room temperature. The resultant APTES-modified P25 TiO2 nanoparticle-coated paper samples exhibit much greater stability to UV-illumination than uncoated blank reference paper. Very little, or no, photo-degradation in terms of brightness and whiteness, respectively, of the P25-TiO2-nanoparticle-treated paper is observed. There are many other potential applications for this Green Chemistry approach to protect cellulosic fibres from UV-bleaching in sunlight and to protect their whiteness and maintain their brightness. © 2014 Elsevier Ltd.