First-Row-Transition Ion Metals(II)-EDTA Functionalized Magnetic Nanoparticles as Catalysts for Solvent-Free Microwave-Induced Oxidation of Alcohols

abstract

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.

keywords

ASSISTED PEROXIDATIVE OXIDATION; AEROBIC OXIDATION; SELECTIVE OXIDATION; FE3O4 NANOPARTICLES; EFFICIENT CATALYST; ORGANIC FRAMEWORKS; NANO-ADSORBENT; REMOVAL; COMPLEXES; MICROSPHERES

subject category

Chemistry

authors

Martins, NMR; Martins, LMDRS; Amorim, CO; Amaral, VS; Pombeiro, AJL

our authors

acknowledgements

This work has been supported by the Foundation for Science and Technology (FCT), Portugal (UID/QUI/00100/2013, PTDC/QEQ-ERQ/1648/2014 and PTDC/QEQ-QIN/3967/2014 projects). NMRM express gratitude to FCT for the PhD CATSUS fellowship (SFRH/BD/52371/2013). Work was also supported by project CICECO-Aveiro Institute of Materials, POCI-01-0145-FEDER-007679 (FCT Ref. UID/CTM/50011/2013), financed by national funds through the FCT/MEC and when appropriate co-financed by FEDER under the PT2020 Partnership Agreement. The authors thank I. Nogueira for the SEM analysis of MicroLab IST.

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