Catalytic oxidation of thioanisole using oxovanadium (IV)‐functionalized electrospun polybenzimidazole nanofibers
- Authors: Walmsley, Ryan S , Hlangothi, Percy , Litwinski, Christian , Nyokong, Tebello , Torto, Nelson , Tshentu, Zenixole R
- Date: 2013
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/242083 , vital:51000 , xlink:href="https://doi.org/10.1002/app.38067"
- Description: Polybenzimidazole fibers, with an average diameter of 262 nm, were produced by the process of electrospinning. These fibers were used as a solid support material for the immobilization of oxovanadium(IV) which was achieved via a reaction with vanadyl sulfate. The oxovanadium(IV)-functionalized nanofibers were used as heterogeneous catalysts for the oxidation of thioanisole under both batch and pseudo-continuous flow conditions with great success. Under batch conditions near quantitative oxidation of thioanisole was achieved in under 90 min, even after four successive catalytic reactions. Under continuous conditions, excellent conversion of thioanisole was maintained throughout the period studied at flow rates of up to 2 mLh−1. This study, therefore, proposes that electrospun polybenzimidazole nanofibers, with their small diameters, impressive chemical and thermal stability, as well as coordinating benzimidazole group, may be a desirable support material for immobilization of homogeneous catalysts.
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Oxovanadium (IV)-containing poly (styrene-co-4′-ethenyl-2-hydroxyphenylimidazole) electrospun nanofibers for the catalytic oxidation of thioanisole
- Authors: Walmsley, Ryan S , Litwinski, Christian , Antunes, Edith M , Hlangothi, Percy , Hosten, Eric C , McCleland, Cedric , Nyokong, Tebello , Torto, Nelson , Tshentu, Zenixole R
- Date: 2013
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241665 , vital:50959 , xlink:href="https://doi.org/10.1016/j.molcata.2013.07.018"
- Description: The catalytic fibers have been fabricated by the electrospinning of a copolymer of styrene and 2-(2′-hydroxy-4′-ethenylphenyl)imidazole {p(ST-co-VPIM)} followed by a reaction with a methanolic vanadyl solution to afford the oxovanadium(IV)-containing poly(styrene-co-4′-ethenyl-2-hydroxyphenylimidazole) fibers {p(ST-co-VPIM)-VO fibers}. The relationship between polymer concentration and fiber diameter was investigated, and at high concentration (20 wt%) the fibers were quite large (average diameter of 3.8 μm) but as the concentration was reduced fibers of much lower diameter were produced (0.6 μm using 8 wt%). The BET surface area for p(ST-co-VPIM) fibers (0.6 μm diameter) was 47.9 m2 g−1 and functionalization of p(ST-co-VPIM) with vanadyl resulted in an increase in surface area to 60.7 m2 g−1 for p(ST-co-VPIM)-VO. The presence of vanadyl was confirmed by XPS and EPR. The EPR spectral analyses depicted complex speciation of vanadium within these polymer supports. These catalytic fibers were applied under batch and continuous flow conditions for the catalytic oxidation of thioanisole using hydrogen peroxide. The continuous flow method gave excellent and constant conversion throughout the 10 h period studied. The leaching of vanadium from the fiber support was 4% over the 10 h period indicating a significant stability of the material.
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Imidazole-functionalized polymer microspheres and fibers–useful materials for immobilization of oxovanadium (IV) catalysts
- Authors: Walmsley, Ryan S , Ogunlaja, Adeniyi S , Coombes, Matthew J , Chidawanyika, Wadzanai J U , Litwinski, Christian , Torto, Nelson , Nyokong, Tebello , Tshentu, Zenixole R
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/246041 , vital:51431 , xlink:href="https://doi.org/10.1039/C2JM15485D"
- Description: Both polymer microspheres and microfibers containing the imidazole functionality have been prepared and used to immobilize oxovanadium(IV). The average diameters and BET surface areas of the microspheres were 322 μm and 155 m2 g−1 while the fibers were 1.85 μm and 52 m2 g−1, respectively. XPS and microanalysis confirmed the incorporation of imidazole and vanadium in the polymeric materials. The catalytic activity of both materials was evaluated using the hydrogen peroxide facilitated oxidation of thioanisole. The microspheres were applied in a typical laboratory batch reactor set-up and quantitative conversions (>99%) were obtained in under 240 min with turn-over frequencies ranging from 21.89 to 265.53 h−1, depending on the quantity of catalyst and temperature. The microspherical catalysts also proved to be recyclable with no drop in activity being observed after three successive reactions. The vanadium functionalized fibers were applied in a pseudo continuous flow set-up. Factors influencing the overall conversion and product selectivity, including flow rate and catalyst quantity, were investigated. At flow rates of 1–4 mL h−1 near quantitative conversion was maintained over an extended period. Keeping the mass of catalyst constant (0.025 g) and varying the flow rate from 1–6 mL h−1 resulted in a shift in the formation of the oxidation product methyl phenyl sulfone from 60.1 to 18.6%.
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Photophysical and photochemical behavior of electrospun fibers of a polyurethane polymer chemically linked to lutetium carboxyphenoxy phthalocyanine
- Authors: Zugle, Ruphino , Litwinski, Christian , Torto, Nelson , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/248428 , vital:51685 , xlink:href="https://doi.org/10.1039/C1NJ20126C"
- Description: A phthalocyanine complex of lutetium substituted with four peripherally substituted 4-carboxyphenoxy groups was synthesized using cyclotetramerisation reaction. Its structure was elucidated using conventional spectroscopic methods and elemental analysis. The spectral behavior of the complex was studied in DMF solution and in a solid polyurethane fiber matrix. The UV-Visible spectrum showed a red shift in its Q-band maximum absorption within the fiber as compared to that in solution. The triplet quantum yield in DMF was determined to be 0.51 with a lifetime of 2.7 μs and a singlet oxygen quantum yield of 0.33 with a lifetime of 19.85 μs in the same solvent. The functionalized phthalocyanine fiber could be a promising fabric material for applications such as self-disinfecting in wound dressing. A method based on the conversion of ADMA was used to estimate the singlet oxygen quantum yield of the Pc in the hybrid fiber. An estimated singlet oxygen quantum yield value of 0.11 in aqueous medium was obtained. The fluorescence quantum yield of the Pc was found to be 0.01 with a lifetime of 3.20 ns in DMF.
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