Papers by Author: João Rocha

Abstract: Mono-substituted and sandwich-type copper substituted polyoxoanions ([PW11CuO39]5− and [Cu4(H2O)2(PW9O34)2]10−) were studied as catalysts for the epoxidation of cyclooctene and geraniol, using the green oxidant H2O2, with the results suggesting good efficiency at room temperature. High selectivity and reasonable conversion data were found after the first minutes of reaction. The copper centre may be responsible for this performance and our on-going research focuses in the preparation of new materials incorporating copper into polyoxometalates (POMs). In this context, we have also isolated a new crystalline dimeric sandwich-type polyoxocoppertungstate {H7.05[Cu3WO(H2O)(CuW9O34)(Cu0.6W9O34)]}7.75−. This compound was isolated as potassium salt and structurally characterized by FTIR and single-crystal X-ray diffraction (XRD). The polyoxoanion is composed by the [CuW9O34]12− and [Cu0.6W9O34]12.8− anionic fragments, joined together by a rhomb-like arrangement of three Cu2+ and one W6+ metallic centres, all exhibiting octahedral coordination geometries.

Abstract: The microporous titanosilicate ETS-10 was subjected to three cycles of ferricinium ion ([(η5-C5H5)2Fe]+, Fc+) exchange by using aqueous solutions of ferricinium hexafluorophosphate and microwave-assisted heating. The resultant hybrid inorganic-organometallic (ETS-10/Fc+) materials were characterised by elemental analysis, ICP-AES, FTIR and Raman spectroscopy, powder X-ray diffraction (XRD), scanning electron microscopy (SEM), diffuse reflectance (DR) UV-Vis, 29Si and 23Na solid-state NMR. The results support the successful inclusion of Fc+ in the pores of the inorganic host by ion exchange of extra-framework sodium and potassium ions.

Abstract: A new porous benzene-silica hybrid clay heterostructure has been prepared by a template-assisted method. The synthesis of Hybrid Porous Clay Heterostructures (HPCH) has been performed via the intercalation of a quaternary ammonium cation surfactant (cetyltrimethylammonium bromide) and a neutral amine (octylamine) as cosurfactant, in a Portuguese clay, to direct the interlamellar hydrolysis and condensation polymerisation of neutral inorganic etraethylorthosilicate (TEOS) together with an organic precursor, the 1,4- bis(triethoxysilyl)benzene (BTEB). The material has been characterised by elemental analysis, powder X-ray diffraction, nitrogen adsorption, 13C CP MAS, 29Si MAS and CP MAS NMR spectroscopy, transmission electron microscopy (TEM), scanning electron microscopy (SEM) and thermal analyses. The hydrophobicity of the material was tested by water adsorption. Its potential application as adsorbent of volatile organic compounds was studied by the adsorption of methanol, methyl ethyl ketone, toluene and trichloroethylene.

Abstract: The thermal transformation of Eu3+-doped and undoped microporous titanosilicate AM-3 has been reported. AM-3 is stable up to 600 °C and transforms into the analogue of the mineral narsarsukite at 800 °C. The narsarsukite obtained from AM-3 is purer than that prepared from the titanosilicates ETS-10, ETS-4 and AM-1, and is suitable for hosting optically-active Ln3+ ions. The materials have been studied by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray spectrometry (EDS), solid-state magic-angle spinning nuclear magnetic resonance (MAS NMR), Raman and photoluminescence pectroscopies.

Abstract: Organically-modified silica xerogels from 3-aminopropyltrimethoxysilane (APTES) and 3-isocyanatepropyltriethoxysilane (ICPTES) have been synthesized through carboxylic acid (formic acid, acetic acid and valeric acid) solvolysis. The resulting hybrid materials have been characterized by powder X-ray diffraction, mid-infrared spectroscopy, 29Si and 13C nuclear magnetic resonance, and photoluminescence spectroscopy. The results show that urea cross-links have been formed in these hybrids. The luminescence features depend on the selected carboxylic acids. For example, comparatively to the hybrids derived from formic and acetic acid solvolysis, valeric acid shows a red-shift of the emission features.