Publications by authors named "Carlos M Granadeiro"

Zinc oxide nanoparticles (ZnO NPs) have been investigated due to their distinct properties, variety of structures and sizes, and mainly for their antimicrobial activity. They have received a positive safety evaluation from the European Food Safety Authority (EFSA) for packaging applications as transparent ultraviolet (UV) light absorbers based on the absence of significant migration of zinc oxide in particulate form. ZnO NPs with different morphologies (spherical, flower, and sheet) have been synthesized via different sol-gel methods and extensively characterized by several solid-state techniques, namely vibrational spectroscopy, powder X-ray diffraction (XRD), scanning electron microscopy/energy dispersive X-ray spectroscopy (SEM/EDS), Fourier Transform Infrared Spectroscopy (FTIR), ultraviolet-visible spectroscopy (UV-VIS), electron paramagnetic resonance (EPR), and nitrogen adsorption-desorption isotherms.

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The adsorptive performance of mesoporous silica-based materials towards inorganic (metal ions) and organic (dyes) water pollutants was investigated. Mesoporous silica materials with different particle size, surface area and pore volume were prepared and tailored with different functional groups. These materials were then characterised by solid-state techniques, namely vibrational spectroscopy, elemental analysis, scanning electron microscopy and nitrogen adsorption-desorption isotherms, allowing the successful preparation and structural modifications of the materials to be confirmed.

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The aquasoluble Fe complexes [Fe(H O) (L )] ⋅ 4H O (Fe1) and [Fe(H O) (L )] ⋅ 3H O (Fe2), bearing the basic forms of 5-chloro-3-(2-(4,4-dimethyl-2,6-dioxocyclohexylidene)hydrazinyl)-2-hydroxy-benzenesulfonic acid (H L ) and 3-(2-(2,4-dioxopentan-3-ylidene)hydrazinyl)-2-hydroxy-5-nitrobenzenesulfonic acid (H L ), were incorporated for the first time into amine-functionalized SBA-15 support via an impregnation method. The successful preparation of the composites was confirmed by Fourier-Transform Infrared spectroscopy (FT-IR), powder X-ray diffraction (XRD), scanning electron microscope (SEM/EDS), transmission electron microscopy (TEM), elemental analysis, and nitrogen adsorption-desorption isotherms. The resulting Fe1@aptesSBA-15 and Fe2@aptesSBA-15 composites were tested as the first SBA-15-based heterogeneous catalysts for the conversion of furfuryl alcohol under mild reaction conditions (80 to 100 °C) and with an environmentally friendly oxidant (TBHP, 70 % aq.

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An effective and sustainable oxidative desulfurization process for treating a multicomponent model fuel was successfully developed using as a heterogeneous catalyst a composite material containing as an active center the europium Lindqvist [Eu(WO)] (abbreviated as EuW) encapsulated into the nanoporous ZIF-8 (zeolitic imidazolate framework) support. The EuW@ZIF-8 composite was obtained through an impregnation procedure, and its successful preparation was confirmed by various characterization techniques (FT-IR, XRD, SEM/EDS, ICP-OES). The catalytic activity of the composite and the isolated EuW was evaluated in the desulfurization of a multicomponent model fuel containing dibenzothiophene derivatives (DBT, 4-MDBT and 4,6-DMDBT) with a total sulfur concentration of 1500 ppm.

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Two quaternary ammonium catalysts based on the monovacant polyoxotungstate ([PWO], abbreviated as PW) were prepared and characterized. The desulfurization performances of the PW-based hybrids (of tetrabutylammonium and trimethyloctadecylammonium, abbreviated as TBA[PW] and ODA[PW], respectively), the corresponding potassium salt (KPWO, abbreviated as KPW) and the peroxo-compound (TBA-PO[WO(O)], abbreviated as TBA[PW]) were compared as catalysts for the oxidative desulfurization of a multicomponent model diesel (2000 ppm S). The oxidative desulfurization studies (ODS) were performed using solvent-free systems and aqueous HO as oxidant.

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The monolacunary Keggin-type [PWO] (PW) heteropolyanion was immobilized on porous framework of mesoporous silicas, namely SBA-15 and an ethylene-bridged periodic mesoporous organosilica (PMOE). The supports were functionalized with a cationic group (-trimethoxysilypropyl--trimethylammonium, TMA) for the successful anchoring of the anionic polyoxometalate. The PW@TMA-SBA-15 and PW@TMA-PMOE composites were evaluated as heterogeneous catalysts in the oxidative desulfurization of a model diesel.

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The employment of -(2-carboxyphenyl)salicylideneimine in 4f metal chemistry has led to two families of dinuclear complexes depending on the lanthanide(III) used. Representative members exhibit interesting magnetic, optical, and catalytic properties.

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Different methodologies were used to increase the oxidative desulfurization efficiency of the Keggin phosphotungstate [PWO] (PW). One possibility was to replace the acid proton by three different ionic liquid cations, forming the novel hybrid polyoxometalates: [BMIM]₃PW (BMIM as 1-butyl-3-methylimidazolium), [BPy]₃PW (BPy as 1-butylpyridinium) and [HDPy]₃PW (HDPy as hexadecylpyridinium. These hybrid Keggin compounds showed high oxidative desulfurization efficiency in the presence of [BMIM]PF₆ solvent, achieving complete desulfurization of multicomponent model diesel (2000 ppm of S) after only 1 h, using a low excess of oxidant (H₂O₂/S = 8) at 70 °C.

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The porous metal-organic framework UiO-66(Zr) obtained via non modulated synthesis, has revealed to be a notable heterogeneous catalyst, enabling extremely fast and very efficient desulfurization of a multicomponent model diesel and also a real diesel fuel.

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A novel method to prepare silica nano-sized particles incorporating polyoxometalates was developed leading to a new efficient heterogeneous oxidative catalyst. Zinc-substituted polyoxotungstate [PW11Zn(H2O)O39](5-) (PW11Zn) was encapsulated into silica nanoparticles using a cross-linked organic-inorganic core, performed through successive spontaneous reactions in water. The potassium salt of PW11Zn and the composite formed, PW11Zn-APTES@SiO2, were characterized by a myriad of solid-state methods such as FT-IR, FT-Raman, (31)P and (13)C CP/MAS solid-state NMR, elemental analysis and SEM-EDS, confirming the integrity of the PW11Zn structure immobilized in the silica nanoparticles.

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The initial employment of di-2-pyridyl ketone azine in 4f metal chemistry has led to a unique ligand transformation; the resulting anionic ligand is able to bridge two Ln(III) ions, affording neutral and cationic dinuclear complexes with interesting properties.

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FT-IR, FT-Raman and surface-enhanced Raman scattering spectra of 5-ethylsulphonyl-2-(o-chlorobenzyl)benzoxazole were recorded and analyzed. The vibrational wavenumbers were examined theoretically using the Gaussian09 set of quantum chemistry codes, and the normal modes were assigned by potential energy distribution calculations. The presence of CH(2), SO(2) and CH(3) modes in the SERS spectrum indicates the nearness of the methyl group to the metal surface which affects the orientation and metal molecule interaction.

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The FT-IR and FT-Raman spectra of 2-phenoxymethylbenzothiazole were recorded and analyzed. The surface enhanced Raman scattering (SERS) spectrum was recorded in a silver colloid. The vibrational wavenumbers of the compound have been computed using the Hartree-Fock/6-31G* basis and compared with the experimental values.

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