TY - JOUR
T1 - MIL-101 promotes the efficient aerobic oxidative desulfurization of dibenzothiophenes
AU - Gómez-Paricio, Adrián
AU - Santiago-Portillo, Andrea
AU - Navalón, Sergio
AU - Concepción, Patricia
AU - Alvaro, Mercedes
AU - Garcia, Hermenegildo
N1 - Publisher Copyright:
© The Royal Society of Chemistry 2016.
Copyright:
Copyright 2020 Elsevier B.V., All rights reserved.
PY - 2016
Y1 - 2016
N2 - MIL-101 promotes aerobic oxidation in n-dodecane of dibenzothiophene (DBT) and its methyl-substituted derivatives to their corresponding sulfones with complete selectivity, without observation of the sulfoxide. DBT sulfones can be completely separated from n-dodecane by water extraction. MIL-101(Cr) without the need of pre-activation was found to be more convenient than the also-active MIL-101(Fe) analog. The reaction exhibits an induction period due to the diffusion inside the pore system of the solvent or oxygen and it is not observed if the MIL-101 sample is first in contact with the solvent at the reaction temperature for a sufficiently long time. MIL-101 is reusable for at least five times without any sign of deactivation according to the time-conversion plots. Evidence by electron paramagnetic resonance spectroscopy detecting the hydroperoxide radical adduct with a spin trapping agent and Raman spectroscopy detection of superoxide supports that the process is an auto-oxidation reaction initiated by MIL-101 following the expected radical chain mechanism inside the MIL-101 cages.
AB - MIL-101 promotes aerobic oxidation in n-dodecane of dibenzothiophene (DBT) and its methyl-substituted derivatives to their corresponding sulfones with complete selectivity, without observation of the sulfoxide. DBT sulfones can be completely separated from n-dodecane by water extraction. MIL-101(Cr) without the need of pre-activation was found to be more convenient than the also-active MIL-101(Fe) analog. The reaction exhibits an induction period due to the diffusion inside the pore system of the solvent or oxygen and it is not observed if the MIL-101 sample is first in contact with the solvent at the reaction temperature for a sufficiently long time. MIL-101 is reusable for at least five times without any sign of deactivation according to the time-conversion plots. Evidence by electron paramagnetic resonance spectroscopy detecting the hydroperoxide radical adduct with a spin trapping agent and Raman spectroscopy detection of superoxide supports that the process is an auto-oxidation reaction initiated by MIL-101 following the expected radical chain mechanism inside the MIL-101 cages.
UR - http://www.scopus.com/inward/record.url?scp=84955250119&partnerID=8YFLogxK
U2 - 10.1039/c5gc00862j
DO - 10.1039/c5gc00862j
M3 - Article
AN - SCOPUS:84955250119
SN - 1463-9262
VL - 18
SP - 508
EP - 515
JO - Green Chemistry
JF - Green Chemistry
IS - 2
ER -