Kinetics and mechanism of the tungsten-catalyzed oxidation of organic sulphides and alkenes by hydrogen peroxide

Arcoria, Antonio; Ballisterri, Francesco Paolo; Tomaselli, Gaetano A.; Furia, Fulvio Di; Modena, G.

doi:10.1016/0304-5102(83)80117-5

Cited by 35 publications

(4 citation statements)

References 12 publications

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“…Most likely, the first step is adsorption on the catalyst surface and formation of moderately electrophilic W and/or Zr (hydro)peroxo species, which can react directly with electron-rich alkenes and thioethers, transferring oxygen (Scheme 2). 12,67,71 In accordance with the literature, 13 Zr hydroperoxo species also interact with H 2 O 2 , producing superoxide radicals and singlet oxygen (Scheme 2).…”

Section: Resultssupporting

confidence: 84%

“…Such moderate selectivity toward sulfoxides points to the mild electrophilicity of the active species and is not typical of homogeneous and supported W-catalysts, which usually produce sulfoxides with the selectivity as high as 82–92% at 92–98% sulphide conversion due to the high electrophilicity of tungsten peroxo complexes. 67–69 On the other hand, in Zr-MOF- 11,14 and Zr–Si-catalysed 17 thioether oxidations, sulfone predominated over sulfoxide even while using an equimolar amount of the oxidant, indicating the nucleophilic character of the oxidising species in these systems.…”

Section: Resultsmentioning

confidence: 99%

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Heterogeneous H₂O₂-based selective oxidations over zirconium tungstate α-ZrW₂O₈

Evtushok,

Ivanchikova,

Zalomaeva

et al. 2024

Dalton Trans.

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Section: Resultssupporting

confidence: 84%

Section: Resultsmentioning

confidence: 99%

Heterogeneous H₂O₂-based selective oxidations over zirconium tungstate α-ZrW₂O₈

Evtushok,

Ivanchikova,

Zalomaeva

et al. 2024

Dalton Trans.

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“…This implies that there is a larger interfacial mass surface area available per unit volume for the transfer of the peroxometal complex from the aqueous to organic phase to occur. In addition, surface renewal was enhanced because there is higher turbulence present at 10 000 rpm, which causes lower mass transfer resistance . On the basis of the high sulfur conversion and kinetic rate constants, the mixer speed of 10 000 rpm has the least mass transfer resistance as a result of the higher turbulence created and high local energy dissipation that created droplets of smaller sizes.…”

Section: Results and Discussionmentioning

confidence: 99%

Kinetics of Mixing-Assisted Oxidative Desulfurization of Dibenzothiophene in Toluene Using a Phosphotungstic Acid/Hydrogen Peroxide System: Effects of Operating Conditions

Luna¹,

Wan

Golosinda³

et al. 2017

Energy Fuels

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Mixing-assisted oxidative desulfurization (MAOD) of model fuel that contains dibenzothiophene (DBT) using phosphotungstic acid (HPW) as a catalyst and hydrogen peroxide (H 2 O 2 ) as an oxidant was evaluated. Characterization analysis of HPW shows that the average crystallite size is 82.39 nm, with a disintegrated structure and morphology. The effect of operating parameters, such as mixer speed (5000−10 000 rpm), tetraoctylammonium bromide [phase-transfer agent (PTA)]/ HPW ratio (0.5:1−5:1), and temperature (25−60 °C), on the sulfur conversion of DBT was examined. Results show that the sulfur conversion increases with an increasing temperature and mixer speed and a lower amount of PTA. The highest sulfur removal and rate constant of 100.0% and 0.1528 min −1 , respectively, were attained under the following conditions: 1:1 ratio, 40 °C, and 10 000 rpm. The pseudo-first-order equation and Arrhenius equation were applied to determine the kinetic rate constant and activation energy of HPW in the oxidation of DBT in a MAOD system. High correlation coefficient values (R 2 ≥ 0.93) indicate that the pseudo-first-order equation has the goodness of fit in describing the experimental kinetic data. Moreover, the activation energy of HPW derived from the Arrhenius equation was 42.60 kJ/mol.

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“…Due to their catalytic activity and specialized redox behavior, peroxotungstates have received special attention in a variety of industrial, pharmaceutical, and biological processes as they can be regarded as an environmentally friendly alternative to traditional oxidation reactions that represents an improvement in terms of pollution prevention 1. They are widely used in stoichiometric as well as catalytic oxidation in organic chemistry,2 for example in the oxidation of alcohols,3,4 internal alkenes,5 amines,6 sulfides,4,7,8 isobutyraldehyde,9 hydroquinones,2 bromide,10 benzyl chlorides,11 epoxidation of chiral allylic alcohols,12 geraniol, linalool13 and also in olefin epoxidations,14–17 such as cyclohexene,18 propylene,19 alkene,20 and cis ‐1‐propenylphosphonic acid 21. To better understand these catalytic processes, a more detailed characterization of peroxotungstates is necessary.…”

Section: Introductionmentioning

confidence: 99%