Solvent-free, heterogeneous photooxygenation of hydrocarbons by Hyflon? membranes embedding a fluorous-tagged decatungstate

Carraro, Mauro; Gardan, Martino; Scorrano, Gianfranco; Drioli, Enrico; Fontananova, Enrica; Bonchio, Marcella

doi:10.1039/b610551c

Cited by 68 publications

(30 citation statements)

References 39 publications

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“…The present results obtained provide a simple route for the preparation of C, N, and S doped TiO 2 with enhanced photocatalytic activity compared to bare TiO 2 under visible light irradiation for EB oxidation to acetophenone. To the best of our knowledge, no report is available in the literature on the photocatalytic oxidation of EB except for two, wherein in one report, environmental impact, high cost, and their hydrothermal and chemical stability are questionable issues [15] and the other one deals with UVactive TiO 2 alone with meager conversion and yields [16]. Based on these reports and building on our previous expertise [7], we report herein the selective activation of benzylic C-H bonds of EB (difficult to oxidize due to the absence of an electrondonating aromatic ring-activation group) to acetophenone and 1-phenylethanol selectively using solar energy (Scheme 1).…”

Section: Introductionmentioning

confidence: 91%

Selective solar photocatalytic oxidation of ethylbenzene on C, N, and S doped TiO2

et al. 2011

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The liquid-phase photo-oxidation of ethylbenzene (EB) is investigated in solar light with air/O 2 /N 2 at atmospheric pressure, in a batch reactor using acetonitrile medium. It is carried out over TiO 2 doped with C, N, and S (TCNS) photocatalyst samples. The photocatalytic oxidation yielded acetophenone (33%) and 1-phenylethanol (21%) at 56% conversion of EB during a 6-h irradiation time. This product distribution indicates that C-H bond activation has occurred only at the alkyl chain. The effects of the EB to water content ratio, amount of photocatalyst and its sustainability, pH, have been studied. It is illustrated that the reaction carried out by this environmentally friendly photocatalysis is truly heterogeneous under mild conditions using solar light and no waste generation. An optimum loading of TCNS5 was observed for the photo-oxidation of EB.

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Section: Introductionmentioning

confidence: 91%

Selective solar photocatalytic oxidation of ethylbenzene on C, N, and S doped TiO2

et al. 2011

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“…Decatungstate has been also heterogenized in membranes made of Hyflon, an amorphous perfluoropolymer [67]. Using the tetrabutylammonium salt of the decatungstate, the formation of irregular catalyst aggregates has been observed because of its low affinity with the polymeric matrix (Fig.…”

Section: Photocatalytic Membrane Reactorsmentioning

confidence: 97%

“…The Hyflon-based catalytic membranes have been used in the solvent-free photooxygenation of benzylic C-H bonds with a turnover number of up to 6100 (calculated as the ration between products (mol) and catalyst (mol)) in 4 h and remarkable alcohol selectivity, thus, providing a convenient alternative to other catalytic systems [67].…”

Section: Photocatalytic Membrane Reactorsmentioning

confidence: 99%

Membrane Reactors: Advanced Systems for Intensified Chemical Processes

Fontananova

Drioli

2014

Chemie Ingenieur Technik

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To realize sustainable growth, the energy demand and environmental impact of chemical processes need to be reduced. Multifunctional membrane reactors (MRs) are a feasible way to shift the industrial catalysis towards novel intensified processes, since they combine a chemical reaction with a membrane-based separation. Compared to traditional, sequential reaction-separation systems, MRs require less energy, show increased productivity and reduced by-product formation, easier down-and up-stream processing, compact process equipment as well as the possibility of heat recovery and catalyst recycling.

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“…For example, the anchorage of a given POM to a solid substrate can lead to the combination of its catalytic activity in homogeneous phase with the ease of recovery and recycling shown by heterogeneous catalysts, which represents a clear demand for industrial purposes [35,36]. Different solid substrates have been employed as POM supports, such as oxides (alumina, silica), metals (silicon, gold), and HOPG [37,38,39,40,41,42,43].…”

Section: Introductionmentioning

confidence: 99%

Immobilization of Polyoxometalates on Tailored Polymeric Surfaces

et al. 2018

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Herein we describe the preparation of hybrid polymer–inorganic interfaces by the immobilization of polyoxometalate nanoclusters on functionalized polymer surfaces. The polymeric surfaces were made of polystyrene-b-poly(acrylic acid)/polystyrene (PS-b-PAA/PS) blends by spin coating on a silicon wafer. The functionalization of the polymer film was obtained by interfacial migration of the amphiphilic block copolymer toward the interface upon water vapor annealing. The carboxylic acid functional groups contained in the PAA block were then employed to anchor the [LnIII(α-SiW11O39)]5− polyoxometalates (Ln: Ce, Er). This purpose was achieved by immersing the films in aqueous solutions of the in situ-formed inorganic nanoclusters. X-ray photoelectron and confocal Raman spectroscopies, together with atomic force microscopy, confirmed the immobilization of the inorganic species at the interface.

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Solvent-free, heterogeneous photooxygenation of hydrocarbons by Hyflon? membranes embedding a fluorous-tagged decatungstate

Abstract: Hybrid fluoropolymeric membranes with 25% loading of the fluorous-tagged (RfN)4W10O32 effect the solvent-free photooxygenation of benzylic C-H bonds with up to 6100 TONs in 4 hours.

Cited by 68 publications

References 39 publications

Selective solar photocatalytic oxidation of ethylbenzene on C, N, and S doped TiO2

Selective solar photocatalytic oxidation of ethylbenzene on C, N, and S doped TiO2

Membrane Reactors: Advanced Systems for Intensified Chemical Processes

Immobilization of Polyoxometalates on Tailored Polymeric Surfaces

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