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Solvent-free microwave-induced oxidation of alcohols catalyzed by ferrite magnetic nanoparticles

Publication . Martins, Nuno; Martins, Luisa; Amorim, Carlos O.; Amaral, Vitor; Pombeiro, Armando

A series of first-row-transition-metal ferrite magnetic nanoparticles (NPs) MFe2O4 [M = Mn2+ (1), Fe2+ (2), Co-2+ (3), Ni2+ (4), Cu2+ (5) or Zn2+ (6)] were prepared by the co-precipitation method and characterized by Fourier transform infrared (FTIR) spectroscopy, powder X-ray diffraction (XRD), scanning electron microscope -energy dispersive X-ray spectrometry (SEM-EDS), vibrating sample magnetometer (VSM) and X-ray photoelectron spectroscopy (XPS). Those NPs were used as catalysts for the microwave-assisted oxidation of various alcohols in solvent-free medium. MnFe2O4 (1), CoFe2O4 (3) and CuFe2O4 (5) act as catalysts for the conversion of alcohols to the corresponding ketones or aldehydes with a yield range of 81 to 94% in 2 h at 120 degrees C using t-BuOOH as an oxidant. These catalysts can be readily isolated by using an external magnet and no significant loss of activity is observed when reused up to 10 consecutive runs. The effects of some parameters, such as temperature, time, type of oxidant and presence of organic radicals, on the oxidation reactions were also investigated. The presented literature overview highlights the advantages of our new 1-6 NPs catalytic systems in terms of efficiency and economy, mainly due the used microwave (MW) heating mode.

2017-07Journal article

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First-row-transition ion metals(II)-EDTA functionalized magnetic nanoparticles as catalysts for solvent-free microwave-induced oxidation of alcohols

Publication . Martins, Nuno; Martins, Luisa; Amorim, Carlos O.; Amaral, Vitor; Pombeiro, Armando

A series of first-row transition-metals combined with ethylenediamine tetraacetic acid (EDTA), as metal-based N,O-chelating ligands, at the surface of ferrite magnetic nanoparticles (MNPs) was prepared by a co-precipitation method. Those EDTA functionalized MNPs with general formula Fe3O4@EDTA-M2+ [M = Mn2+ (1), Fe2+ (2), Co2+ (3), Ni2+ (4), Cu2+ (5) or Zn2+ (6)] were characterized by FTIR (Fourier Transform Infrared) spectroscopy, powder XRD (X-ray Diffraction), SEM (Scanning Electron Microscope), EDS (Energy Dispersive Spectrometer), VSM (Vibrating Sample Magnetometer) and TGA (Thermal Gravity Analysis). The application of the magnetic NPs towards the microwave-assisted oxidation of several alcohol substrates in a solvent-free medium was evaluated. The influence of reaction parameters such as temperature, time, type of oxidant, and presence of organic radicals was investigated. This study demonstrates that these MNPs can act as efficient catalysts for the conversion of alcohols to the corresponding ketones or aldehydes with high selectivity and yields up to 99% after 2 h of reaction at 110 degrees C using t-BuOOH as oxidant. Moreover, they have the advantage of being magnetically recoverable catalysts that can be easily recycled in following runs.

2017-11Journal article

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Mesoporous nanosilica-supported polyoxomolybdate as catalysts for sustainable desulfurization

Publication . Mirante, Fátima; Gomes, Neide; Branco, Luis; Cunha-Silva, Luís; Almeida, Pedro L.; Pillinger, Martyn; Gago, S.; Granadeiro, Carlos; Balula, Salete

Mesoporous silica nanoparticles (MSNs) strategically functionalized were used to immobilize a homogeneous polyoxomolybdate catalyst [PMo12O40](3-) (PMo12), active but unstable. The PMo12@TBA-MSN composite (where TBA refers to surface-tethered tributylammonium groups) conferred high stability to the polyoxomolybdate catalytic center and displayed an increase in efficiency for the oxidative desulfurization (ECODS) of a diesel simulant under sustainable conditions (using H2O2 as oxidant and an ionic liquid, [BMIM]PF6, as solvent). Continuous reuse of the catalyst and ionic liquid solvent in consecutive ECODS cycles was successfully performed, avoiding the production of residual wastes. The performance of the PMo12@TBA-MSN catalyst improved upon its reuse, leading to complete desulfurization of a multicomponent model diesel containing benzothiophene derivatives after just 1 h of the catalytic stage of the process. The robust nature of the supported catalyst was indicated by characterization of the recovered solid which showed retention of the structural and chemical integrities.

2019-02Journal article

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