Imidazole-functionalized polymer microspheres and fibers–useful materials for immobilization of oxovanadium (IV) catalysts
- Walmsley, Ryan S, Ogunlaja, Adeniyi S, Coombes, Matthew J, Chidawanyika, Wadzanai J U, Litwinski, Christian, Torto, Nelson, Nyokong, Tebello, Tshentu, Zenixole R
- 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%.
- Full Text:
- Date Issued: 2012
- 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%.
- Full Text:
- Date Issued: 2012
Tetra and octa (2, 6-di-iso-propylphenoxy)-substituted phthalocyanines
- Tuhl, Ahmad, Chidawanayika, Wadzanai J U, Ibrahim, Hamada Mohamed, Al-Awadi, Nouria, Litwinski, Christian, Nyokong, Tebello, Behbehani, Haider, Manaa, Hacene, Makhseed, Saad
- Authors: Tuhl, Ahmad , Chidawanayika, Wadzanai J U , Ibrahim, Hamada Mohamed , Al-Awadi, Nouria , Litwinski, Christian , Nyokong, Tebello , Behbehani, Haider , Manaa, Hacene , Makhseed, Saad
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/245855 , vital:51411 , xlink:href="https://doi.org/10.1142/S1088424612004495"
- Description: This work reports on the synthesis of novel metal free, zinc, aluminum, gallium and indium tetra and octa (2,6-di-iso-propylphenoxy)-substituted phthalocyanine derivatives. UV-visible and 1H NMR analyses confirm that a non-planar conformation, adapted by the phenoxy substituents due to steric interaction in both derivative series, perfectly discourage cofacial aggregation. Fluorescence quantum yields vary as a function of the number of substituents on the ring periphery, while the fluorescence lifetimes display no distinct trend. Triplet quantum yields are significantly larger for the tetra 2,6-di-iso-propylphenoxy- substituted derivatives relative to their corresponding octa-substituted species. However there was no overall trend in the triplet lifetime values. For almost all of the phthalocyanine derivatives, singlet oxygen was produced with relatively good quantum yields. This study explores the possibility of fine-tuning their physicochemical properties by simple structural modification.
- Full Text:
- Date Issued: 2012
- Authors: Tuhl, Ahmad , Chidawanayika, Wadzanai J U , Ibrahim, Hamada Mohamed , Al-Awadi, Nouria , Litwinski, Christian , Nyokong, Tebello , Behbehani, Haider , Manaa, Hacene , Makhseed, Saad
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/245855 , vital:51411 , xlink:href="https://doi.org/10.1142/S1088424612004495"
- Description: This work reports on the synthesis of novel metal free, zinc, aluminum, gallium and indium tetra and octa (2,6-di-iso-propylphenoxy)-substituted phthalocyanine derivatives. UV-visible and 1H NMR analyses confirm that a non-planar conformation, adapted by the phenoxy substituents due to steric interaction in both derivative series, perfectly discourage cofacial aggregation. Fluorescence quantum yields vary as a function of the number of substituents on the ring periphery, while the fluorescence lifetimes display no distinct trend. Triplet quantum yields are significantly larger for the tetra 2,6-di-iso-propylphenoxy- substituted derivatives relative to their corresponding octa-substituted species. However there was no overall trend in the triplet lifetime values. For almost all of the phthalocyanine derivatives, singlet oxygen was produced with relatively good quantum yields. This study explores the possibility of fine-tuning their physicochemical properties by simple structural modification.
- Full Text:
- Date Issued: 2012
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