Adsorption and separation of platinum and palladium by polyamine functionalized polystyrene-based beads and nanofibers
- Fayemi, Omolola E, Ogunlaja, Adeniyi S, Kempgens, Pierre F M, Antunes, Edith M, Torto, Nelson, Nyokong, Tebello, Tshentu, Zenixole R
- Authors: Fayemi, Omolola E , Ogunlaja, Adeniyi S , Kempgens, Pierre F M , Antunes, Edith M , Torto, Nelson , Nyokong, Tebello , Tshentu, Zenixole R
- Date: 2013
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241694 , vital:50961 , xlink:href="https://doi.org/10.1016/j.mineng.2013.06.006"
- Description: Adsorption and separation of platinum and palladium chlorido species (PtCl62- and PdCl42-) on polystyrene beads as well as nanofibers functionalized with ammonium centres based on ethylenediamine (EDA), diethylenetriamine (DETA), triethylenetetramine (TETA) and tris-(2-aminoethyl)amine (TAEA) are described. The functionalized sorbent materials were characterized by microanalysis, SEM, XPS, BET and FTIR. The surface area of the functionalized fibers was in the range 69–241 m2/g while it was 73–107 m2/g for the beads. The adsorption and loading capacities of the sorption materials were investigated using both the batch and column studies at 1 M HCl concentration. The adsorption studies for both PtCl62- and PdCl42- on the different sorbent materials fit the Langmuir isotherm with R2 values >0.99. The highest loading capacity of Pt and Pd were 7.4 mg/g and 4.3 mg/g respectively for the nanofiber sorbent material based on ethylenediamine (EDA) while the beads with ethylenediamine (EDA) gave 1.0 mg/g and 0.2 mg/g for Pt and Pd respectively. Metals loaded on the sorbent materials were recovered by using 3% m/v thiourea solution as the eluting agent with quantitative desorption efficiency under the selected experimental conditions. Separation of platinum from palladium was partially achieved by selective stripping of PtCl62- with 0.5 M of NaClO4 in 1.0 M HCl while PdCl42- was eluted with 0.5 M thiourea in 1.0 M HCl. Separation of platinum from iridium and rhodium under 1 M HCl concentration was successful on triethylenetriamine (TETA)-functionalized Merrifield beads. This material (M-TETA) showed selectivity for platinum albeit the low loading capacity.
- Full Text:
- Date Issued: 2013
- Authors: Fayemi, Omolola E , Ogunlaja, Adeniyi S , Kempgens, Pierre F M , Antunes, Edith M , Torto, Nelson , Nyokong, Tebello , Tshentu, Zenixole R
- Date: 2013
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241694 , vital:50961 , xlink:href="https://doi.org/10.1016/j.mineng.2013.06.006"
- Description: Adsorption and separation of platinum and palladium chlorido species (PtCl62- and PdCl42-) on polystyrene beads as well as nanofibers functionalized with ammonium centres based on ethylenediamine (EDA), diethylenetriamine (DETA), triethylenetetramine (TETA) and tris-(2-aminoethyl)amine (TAEA) are described. The functionalized sorbent materials were characterized by microanalysis, SEM, XPS, BET and FTIR. The surface area of the functionalized fibers was in the range 69–241 m2/g while it was 73–107 m2/g for the beads. The adsorption and loading capacities of the sorption materials were investigated using both the batch and column studies at 1 M HCl concentration. The adsorption studies for both PtCl62- and PdCl42- on the different sorbent materials fit the Langmuir isotherm with R2 values >0.99. The highest loading capacity of Pt and Pd were 7.4 mg/g and 4.3 mg/g respectively for the nanofiber sorbent material based on ethylenediamine (EDA) while the beads with ethylenediamine (EDA) gave 1.0 mg/g and 0.2 mg/g for Pt and Pd respectively. Metals loaded on the sorbent materials were recovered by using 3% m/v thiourea solution as the eluting agent with quantitative desorption efficiency under the selected experimental conditions. Separation of platinum from palladium was partially achieved by selective stripping of PtCl62- with 0.5 M of NaClO4 in 1.0 M HCl while PdCl42- was eluted with 0.5 M thiourea in 1.0 M HCl. Separation of platinum from iridium and rhodium under 1 M HCl concentration was successful on triethylenetriamine (TETA)-functionalized Merrifield beads. This material (M-TETA) showed selectivity for platinum albeit the low loading capacity.
- Full Text:
- Date Issued: 2013
Catalytic oxidation of thioanisole using oxovanadium (IV)‐functionalized electrospun polybenzimidazole nanofibers
- Walmsley, Ryan S, Hlangothi, Percy, Litwinski, Christian, Nyokong, Tebello, Torto, Nelson, Tshentu, Zenixole R
- 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.
- Full Text:
- Date Issued: 2013
- 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.
- Full Text:
- Date Issued: 2013
Oxovanadium (IV)-containing poly (styrene-co-4′-ethenyl-2-hydroxyphenylimidazole) electrospun nanofibers for the catalytic oxidation of thioanisole
- Walmsley, Ryan S, Litwinski, Christian, Antunes, Edith M, Hlangothi, Percy, Hosten, Eric C, McCleland, Cedric, Nyokong, Tebello, Torto, Nelson, Tshentu, Zenixole R
- 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.
- Full Text:
- Date Issued: 2013
- 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.
- Full Text:
- Date Issued: 2013
The development of catalytic oxovanadium (IV)-containing microspheres for the oxidation of various organosulfur compounds
- Ogunlaja, Adeniyi S, Khene, Samson M, Antunes, Edith M, Nyokong, Tebello, Torto, Nelson, Tshentu, Zenixole R
- Authors: Ogunlaja, Adeniyi S , Khene, Samson M , Antunes, Edith M , Nyokong, Tebello , Torto, Nelson , Tshentu, Zenixole R
- Date: 2013
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241783 , vital:50969 , xlink:href="https://doi.org/10.1016/j.apcata.2013.05.004"
- Description: The development of poly[allylSB-co-EGDMA] beads containing a tetradentate ligand was achieved via suspension polymerization. The catalyst poly[allylSB-co-EGDMA]-VO was synthesized by reacting VIVOSO4 with poly[allylSB-co-EGDMA]. XPS and EPR were used to confirm the presence of vanadium (V4+) on the beads. The synthesized catalyst (poly[allylSB-co-EGDMA]-VO) was found to have a BET surface area of 22 m2 g−1 and porosity of 135 Å, with the atomic force microscopy (AFM) showing more insight on the porous nature of the beads. Oxidation of thiophene (TH), benzothiophene (BT), dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT) was carried out using tert-butyl hydroperoxide (t-BuOOH) as oxidant. An overall conversion of 60%, 82%, 98% and 87% was achieved for thiophene (TH), benzothiophene (BT), dibenzothiophene (DBT) and 4,6 dimethyldibenzothiophene (4,6-DMDBT) respectively at higher (t-BuOOH) to substrate ratio and at a temperature of 40 °C. The efficient oxidation of the various organosulfur compounds presents potential for the possible application of this catalyst in oxidative desulfurization (ODS) of crude oil.
- Full Text:
- Date Issued: 2013
- Authors: Ogunlaja, Adeniyi S , Khene, Samson M , Antunes, Edith M , Nyokong, Tebello , Torto, Nelson , Tshentu, Zenixole R
- Date: 2013
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241783 , vital:50969 , xlink:href="https://doi.org/10.1016/j.apcata.2013.05.004"
- Description: The development of poly[allylSB-co-EGDMA] beads containing a tetradentate ligand was achieved via suspension polymerization. The catalyst poly[allylSB-co-EGDMA]-VO was synthesized by reacting VIVOSO4 with poly[allylSB-co-EGDMA]. XPS and EPR were used to confirm the presence of vanadium (V4+) on the beads. The synthesized catalyst (poly[allylSB-co-EGDMA]-VO) was found to have a BET surface area of 22 m2 g−1 and porosity of 135 Å, with the atomic force microscopy (AFM) showing more insight on the porous nature of the beads. Oxidation of thiophene (TH), benzothiophene (BT), dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT) was carried out using tert-butyl hydroperoxide (t-BuOOH) as oxidant. An overall conversion of 60%, 82%, 98% and 87% was achieved for thiophene (TH), benzothiophene (BT), dibenzothiophene (DBT) and 4,6 dimethyldibenzothiophene (4,6-DMDBT) respectively at higher (t-BuOOH) to substrate ratio and at a temperature of 40 °C. The efficient oxidation of the various organosulfur compounds presents potential for the possible application of this catalyst in oxidative desulfurization (ODS) of crude oil.
- Full Text:
- Date Issued: 2013
A highly selective and sensitive pyridylazo-2-naphthol-poly (acrylic acid) functionalized electrospun nanofiber fluorescence “turn-off” chemosensory system for Ni 2+
- Adewuyi, Sheriff, Ondigo, Dezzline A, Zugle, Ruphino, Tshentu, Zenixole R, Nyokong, Tebello, Torto, Nelson
- Authors: Adewuyi, Sheriff , Ondigo, Dezzline A , Zugle, Ruphino , Tshentu, Zenixole R , Nyokong, Tebello , Torto, Nelson
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/246012 , vital:51428 , xlink:href="https://doi.org/10.1039/C2AY25182E"
- Description: A fluorescent nanofiber probe for the determination of Ni2+ was developed via the electrospinning of a covalently functionalized pyridylazo-2-naphthol-poly(acrylic acid) polymer. Fluorescent nanofibers with diameters in the range 230–800 nm were produced with uniformly dispersed fluorophores. The excitation and emission fluorescence were at wavelengths 479 and 557 nm respectively, thereby exhibiting a good Stokes' shift. This Ni2+ probe that employs fluorescence quenching in a solid receptor–fluorophore system exhibited a good correlation between the fluorescence intensity and nickel concentration up to 1.0 μg mL−1 based on the Stern–Volmer mechanism. The probe achieved a detection limit (3δ/S) of 0.07 ng mL−1 and a precision, calculated as a relative standard deviation (RSD) of more than 4% (n = 8). The concentration of Ni2+ in a certified reference material (SEP-3) was found to be 0.8986 μg mL−1, which is significantly comparable with the certified value of 0.8980 μg mL−1. The accuracy of the determinations, expressed as a relative error between the certified and the observed values of certified reference groundwater was ≤0.1%. The versatility of the nanofiber probe was demonstrated by affording simple, rapid and selective detection of Ni2+ in the presence of other competing metal ions by direct analysis, without employing any further sample handling steps.
- Full Text:
- Date Issued: 2012
- Authors: Adewuyi, Sheriff , Ondigo, Dezzline A , Zugle, Ruphino , Tshentu, Zenixole R , Nyokong, Tebello , Torto, Nelson
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/246012 , vital:51428 , xlink:href="https://doi.org/10.1039/C2AY25182E"
- Description: A fluorescent nanofiber probe for the determination of Ni2+ was developed via the electrospinning of a covalently functionalized pyridylazo-2-naphthol-poly(acrylic acid) polymer. Fluorescent nanofibers with diameters in the range 230–800 nm were produced with uniformly dispersed fluorophores. The excitation and emission fluorescence were at wavelengths 479 and 557 nm respectively, thereby exhibiting a good Stokes' shift. This Ni2+ probe that employs fluorescence quenching in a solid receptor–fluorophore system exhibited a good correlation between the fluorescence intensity and nickel concentration up to 1.0 μg mL−1 based on the Stern–Volmer mechanism. The probe achieved a detection limit (3δ/S) of 0.07 ng mL−1 and a precision, calculated as a relative standard deviation (RSD) of more than 4% (n = 8). The concentration of Ni2+ in a certified reference material (SEP-3) was found to be 0.8986 μg mL−1, which is significantly comparable with the certified value of 0.8980 μg mL−1. The accuracy of the determinations, expressed as a relative error between the certified and the observed values of certified reference groundwater was ≤0.1%. The versatility of the nanofiber probe was demonstrated by affording simple, rapid and selective detection of Ni2+ in the presence of other competing metal ions by direct analysis, without employing any further sample handling steps.
- Full Text:
- Date Issued: 2012
An ion-imprinted polymer for the selective extraction of mercury(II) ions in aqueous media
- Batlokwa, Bareki Shima, Chimuka, Luke, Tshentu, Zenixole R, Cukrowska, Ewa, Torto, Nelson
- Authors: Batlokwa, Bareki Shima , Chimuka, Luke , Tshentu, Zenixole R , Cukrowska, Ewa , Torto, Nelson
- Date: 2012
- Language: English
- Type: Article
- Identifier: vital:6566 , http://hdl.handle.net/10962/d1004125
- Description: A double-imprinted polymer exhibiting high sensitivity for mercury(II) in aqueous solution is presented. Polymer particles imprinted with mercury(II) were synthesised by copolymerising the functional and cross-linking monomers, N’–[3– (Trimethoxysilyl)–propyl]diethylenetriamine (TPET) and tetraethylorthosilicate (TEOS). A double-imprinting procedure employing hexadecyltrimethylammonium bromide (CTAB), as a second template to improve the efficiency of the polymer, was adopted. The imprinted polymer was characterised by FTIR, scanning electron microscopy (SEM) and the average size determined by screen analysis using standard test sieves. Relative selective coefficients (k`) of the imprinted polymer evaluated from selective binding studies between Hg2+ and Cu2+ or Hg2+ and Cd2+ were 10 588 and 3 147, respectively. These values indicated highly-favoured Hg2+ extractions over the 2 competing ions. The results of spiked and real water samples showed high extraction efficiencies of Hg2+ ions, (over 84%) as evaluated from the detected unextracted Hg2+ ions by ICP-OES. The method exhibited a dynamic response concentration range for Hg2+ between 0.01 and 20 μg/mℓ, with a detection limit (LOD, 3σ) of 0.000036 μg/mℓ (36 ng/ℓ) that meets the monitoring requirements for the USA EPA of 2 000 ng/ℓ for Hg2+ in drinking water. Generally, the data (n=10) had percentage relative standard deviations (%RSD) of less than 4%. Satisfactory results were also obtained when the prepared sorbent was applied for the pre-concentration of Hg2+ from an aqueous certified reference material. These findings indicate that the double-imprinted polymer has potential to be used as an efficient extraction material for the selective pre–concentration of mercury(II) ions in aqueous environments.
- Full Text:
- Date Issued: 2012
- Authors: Batlokwa, Bareki Shima , Chimuka, Luke , Tshentu, Zenixole R , Cukrowska, Ewa , Torto, Nelson
- Date: 2012
- Language: English
- Type: Article
- Identifier: vital:6566 , http://hdl.handle.net/10962/d1004125
- Description: A double-imprinted polymer exhibiting high sensitivity for mercury(II) in aqueous solution is presented. Polymer particles imprinted with mercury(II) were synthesised by copolymerising the functional and cross-linking monomers, N’–[3– (Trimethoxysilyl)–propyl]diethylenetriamine (TPET) and tetraethylorthosilicate (TEOS). A double-imprinting procedure employing hexadecyltrimethylammonium bromide (CTAB), as a second template to improve the efficiency of the polymer, was adopted. The imprinted polymer was characterised by FTIR, scanning electron microscopy (SEM) and the average size determined by screen analysis using standard test sieves. Relative selective coefficients (k`) of the imprinted polymer evaluated from selective binding studies between Hg2+ and Cu2+ or Hg2+ and Cd2+ were 10 588 and 3 147, respectively. These values indicated highly-favoured Hg2+ extractions over the 2 competing ions. The results of spiked and real water samples showed high extraction efficiencies of Hg2+ ions, (over 84%) as evaluated from the detected unextracted Hg2+ ions by ICP-OES. The method exhibited a dynamic response concentration range for Hg2+ between 0.01 and 20 μg/mℓ, with a detection limit (LOD, 3σ) of 0.000036 μg/mℓ (36 ng/ℓ) that meets the monitoring requirements for the USA EPA of 2 000 ng/ℓ for Hg2+ in drinking water. Generally, the data (n=10) had percentage relative standard deviations (%RSD) of less than 4%. Satisfactory results were also obtained when the prepared sorbent was applied for the pre-concentration of Hg2+ from an aqueous certified reference material. These findings indicate that the double-imprinted polymer has potential to be used as an efficient extraction material for the selective pre–concentration of mercury(II) ions in aqueous environments.
- Full Text:
- Date Issued: 2012
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
Oxovanadium (IV)-catalysed oxidation of dibenzothiophene and 4, 6-dimethyldibenzothiophene
- Ogunlaja, Adeniyi S, Chidawanyika, Wadzanai J U, Antunes, Edith M, Fernandes, Manuel A, Nyokong, Tebello, Torto, Nelson, Tshentu, Zenixole R
- Authors: Ogunlaja, Adeniyi S , Chidawanyika, Wadzanai J U , Antunes, Edith M , Fernandes, Manuel A , Nyokong, Tebello , Torto, Nelson , Tshentu, Zenixole R
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/246025 , vital:51429 , xlink:href="https://doi.org/10.1039/C2DT31433A"
- Description: The reaction between [VIVOSO4] and the tetradentate N2O2-donor Schiff base ligand, N,N-bis(o-hydroxybenzaldehyde)phenylenediamine (sal-HBPD), obtained by the condensation of salicylaldehyde and o-phenylenediamine in a molar ratio of 2 : 1 respectively, resulted in the formation of [VIVO(sal-HBPD)]. The molecular structure of [VIVO(sal-HBPD)] was determined by single crystal X-ray diffraction, and confirmed the distorted square pyramidal geometry of the complex with the N2O2 binding mode of the tetradentate ligand. The formation of the polymer-supported p[VIVO(sal-AHBPD)] proceeded via the nitrosation of sal-HBPD, followed by the reduction with hydrogen to form an amine group that was then linked to Merrifield beads followed by the reaction with [VIVOSO4]. XPS and EPR were used to confirm the presence of oxovanadium(IV) within the beads. The BET surface area and porosity of the heterogeneous catalyst p[VIVO(sal-AHBPD)] were found to be 6.9 m2 g−1 and 180.8 Å respectively. Microanalysis, TG, UV-Vis and FT-IR were used for further characterization of both [VIVO(sal-HBPD)] and p[VIVO(sal-AHBPD)]. Oxidation of dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT) was investigated using [VIVO(sal-HBPD)] and p[VIVO(sal-AHBPD)] as catalysts. Progress for oxidation of these model compounds was monitored with a gas chromatograph fitted with a flame ionization detector. The oxidation products were characterized using gas chromatography-mass spectrometry, microanalysis and NMR. Dibenzothiophene sulfone (DBTO2) and 4,6-dimethyldibenzothiophene sulfone (4,6-DMDBTO2) were found to be the main products of oxidation. Oxovanadium(IV) Schiff base microspherical beads, p[VIVO(sal-AHBPD)], were able to catalyse the oxidation of sulfur in dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT) to a tune of 88.0% and 71.8% respectively after 3 h at 40 °C. These oxidation results show promise for potential application of this catalyst in the oxidative desulfurization of crude oils.
- Full Text:
- Date Issued: 2012
- Authors: Ogunlaja, Adeniyi S , Chidawanyika, Wadzanai J U , Antunes, Edith M , Fernandes, Manuel A , Nyokong, Tebello , Torto, Nelson , Tshentu, Zenixole R
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/246025 , vital:51429 , xlink:href="https://doi.org/10.1039/C2DT31433A"
- Description: The reaction between [VIVOSO4] and the tetradentate N2O2-donor Schiff base ligand, N,N-bis(o-hydroxybenzaldehyde)phenylenediamine (sal-HBPD), obtained by the condensation of salicylaldehyde and o-phenylenediamine in a molar ratio of 2 : 1 respectively, resulted in the formation of [VIVO(sal-HBPD)]. The molecular structure of [VIVO(sal-HBPD)] was determined by single crystal X-ray diffraction, and confirmed the distorted square pyramidal geometry of the complex with the N2O2 binding mode of the tetradentate ligand. The formation of the polymer-supported p[VIVO(sal-AHBPD)] proceeded via the nitrosation of sal-HBPD, followed by the reduction with hydrogen to form an amine group that was then linked to Merrifield beads followed by the reaction with [VIVOSO4]. XPS and EPR were used to confirm the presence of oxovanadium(IV) within the beads. The BET surface area and porosity of the heterogeneous catalyst p[VIVO(sal-AHBPD)] were found to be 6.9 m2 g−1 and 180.8 Å respectively. Microanalysis, TG, UV-Vis and FT-IR were used for further characterization of both [VIVO(sal-HBPD)] and p[VIVO(sal-AHBPD)]. Oxidation of dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT) was investigated using [VIVO(sal-HBPD)] and p[VIVO(sal-AHBPD)] as catalysts. Progress for oxidation of these model compounds was monitored with a gas chromatograph fitted with a flame ionization detector. The oxidation products were characterized using gas chromatography-mass spectrometry, microanalysis and NMR. Dibenzothiophene sulfone (DBTO2) and 4,6-dimethyldibenzothiophene sulfone (4,6-DMDBTO2) were found to be the main products of oxidation. Oxovanadium(IV) Schiff base microspherical beads, p[VIVO(sal-AHBPD)], were able to catalyse the oxidation of sulfur in dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT) to a tune of 88.0% and 71.8% respectively after 3 h at 40 °C. These oxidation results show promise for potential application of this catalyst in the oxidative desulfurization of crude oils.
- Full Text:
- Date Issued: 2012
Syntheses, protonation constants and antimicrobial activity of 2-substituted N-alkylimidazole derivatives
- Kleyi, Phumelele, Walmsley, Ryan S, Gundhla, Isaac Z, Walmsley, Tara A, Jauka, Tembisa I, Dames, Joanna F, Walker, Roderick B, Torto, Nelson, Tshentu, Zenixole R
- Authors: Kleyi, Phumelele , Walmsley, Ryan S , Gundhla, Isaac Z , Walmsley, Tara A , Jauka, Tembisa I , Dames, Joanna F , Walker, Roderick B , Torto, Nelson , Tshentu, Zenixole R
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/184066 , vital:44165 , xlink:href="https://www.ajol.info/index.php/sajc/article/view/123858"
- Description: A series of N-alkylimidazole-2-carboxylic acid, N-alkylimidazole-2-carboxaldehyde and N-alkylimidazole-2-methanol derivatives [alkyl = benzyl, methyl, ethyl, propyl, butyl, heptyl, octyl and decyl] have been synthesized and the protonation constants determined. The antimicrobial properties of the compounds were tested against Gram-negative (Escherichi coli), Gram-positive (Staphylococcus aureus and Bacillus subtilis subsp. spizizenii) bacterial strains and yeast (C. albicans). Both the disk diffusion and broth microdilution methods for testing the antimicrobial activity showed that N-alkylation of imidazole with longer alkyl chains and the substitution with low pKa group at 2-position resulted in enhanced antimicrobial activity. Particularly, the N-alkylimidazole-2-carboxylic acids exhibited the best antimicrobial activity due to the low pKa of the carboxylic acid moiety. Generally, all the N-alkylimidazole derivatives were most active against the Gram-positive bacteria [S. aureus (MIC = 5–160 µg mL–1) and B. subtilis subsp. spizizenii (5–20 µg mL–1)], with the latter more susceptible. All the compounds showed poor antimicrobial activity against both Gram-negative (E. coli, MIC = 0.15 to >2500 µg mL–1) bacteria and all the compounds were inactive against the yeast (Candida albicans).
- Full Text:
- Date Issued: 2012
- Authors: Kleyi, Phumelele , Walmsley, Ryan S , Gundhla, Isaac Z , Walmsley, Tara A , Jauka, Tembisa I , Dames, Joanna F , Walker, Roderick B , Torto, Nelson , Tshentu, Zenixole R
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/184066 , vital:44165 , xlink:href="https://www.ajol.info/index.php/sajc/article/view/123858"
- Description: A series of N-alkylimidazole-2-carboxylic acid, N-alkylimidazole-2-carboxaldehyde and N-alkylimidazole-2-methanol derivatives [alkyl = benzyl, methyl, ethyl, propyl, butyl, heptyl, octyl and decyl] have been synthesized and the protonation constants determined. The antimicrobial properties of the compounds were tested against Gram-negative (Escherichi coli), Gram-positive (Staphylococcus aureus and Bacillus subtilis subsp. spizizenii) bacterial strains and yeast (C. albicans). Both the disk diffusion and broth microdilution methods for testing the antimicrobial activity showed that N-alkylation of imidazole with longer alkyl chains and the substitution with low pKa group at 2-position resulted in enhanced antimicrobial activity. Particularly, the N-alkylimidazole-2-carboxylic acids exhibited the best antimicrobial activity due to the low pKa of the carboxylic acid moiety. Generally, all the N-alkylimidazole derivatives were most active against the Gram-positive bacteria [S. aureus (MIC = 5–160 µg mL–1) and B. subtilis subsp. spizizenii (5–20 µg mL–1)], with the latter more susceptible. All the compounds showed poor antimicrobial activity against both Gram-negative (E. coli, MIC = 0.15 to >2500 µg mL–1) bacteria and all the compounds were inactive against the yeast (Candida albicans).
- Full Text:
- Date Issued: 2012
Dimethylglyoxime based ion-imprinted polymer for the determination of Ni(II) ions from aqueous samples
- Rammika, Modise, Darko, Godfrey, Tshentu, Zenixole R, Sewry, Joyce D, Torto, Nelson
- Authors: Rammika, Modise , Darko, Godfrey , Tshentu, Zenixole R , Sewry, Joyce D , Torto, Nelson
- Date: 2011
- Language: English
- Type: Article
- Identifier: vital:6590 , http://hdl.handle.net/10962/d1004173
- Description: A Ni(II)-dimethylglyoxime ion-imprinted polymer {Ni(II)-DMG IIP} was synthesised by the bulk polymerisation method. The morphology of the Ni(II)-DMG IIP and non-imprinted polymer were observed by scanning electron microscopy and the chemical structures were evaluated by infrared spectroscopy. Selectivity of the Ni(II)-DMG IIP was studied by analysing, using an inductively coupled plasma-optical emission spectrometer, for Ni(II) ions that were spiked with varying concentrations of Co(II), Cu(II), Zn(II), Pd(II), Fe(II), Ca(II), Mg(II), Na(I) and K(I) in aqueous samples. The studies revealed Ni(II) recoveries ranging from 93 to 100% in aqueous solutions with minimal interference from competing ions. Enrichment factors ranged from 2 to 18 with a binding capacity of 120 μg∙g−1. Co(II) was the only ion found to slightly interfere with the determination of Ni(II). Selectivity studies confirmed that the Ni(II)-DMG IIP had very good selectivity, characterised by %RSD of less than 5%. The limits of detection and quantification were 3x10-4 μg∙mℓ−1 and 9x10-4 μg∙mℓ−1, respectively. The accuracy of the method was validated by analysing a custom solution of certified reference material (SEP-3) and the concentration of Ni(II) obtained was in close agreement with the certified one. The Ni(II)-DMG IIP was successfully employed to trap Ni(II) ions from a matrix of sea, river and sewage water. It is believed that the Ni(II)-DMG IIP has potential to be used as sorbent material for pre-concentration of Ni(II) ions from aqueous solutions by solid-phase extraction.
- Full Text:
- Date Issued: 2011
- Authors: Rammika, Modise , Darko, Godfrey , Tshentu, Zenixole R , Sewry, Joyce D , Torto, Nelson
- Date: 2011
- Language: English
- Type: Article
- Identifier: vital:6590 , http://hdl.handle.net/10962/d1004173
- Description: A Ni(II)-dimethylglyoxime ion-imprinted polymer {Ni(II)-DMG IIP} was synthesised by the bulk polymerisation method. The morphology of the Ni(II)-DMG IIP and non-imprinted polymer were observed by scanning electron microscopy and the chemical structures were evaluated by infrared spectroscopy. Selectivity of the Ni(II)-DMG IIP was studied by analysing, using an inductively coupled plasma-optical emission spectrometer, for Ni(II) ions that were spiked with varying concentrations of Co(II), Cu(II), Zn(II), Pd(II), Fe(II), Ca(II), Mg(II), Na(I) and K(I) in aqueous samples. The studies revealed Ni(II) recoveries ranging from 93 to 100% in aqueous solutions with minimal interference from competing ions. Enrichment factors ranged from 2 to 18 with a binding capacity of 120 μg∙g−1. Co(II) was the only ion found to slightly interfere with the determination of Ni(II). Selectivity studies confirmed that the Ni(II)-DMG IIP had very good selectivity, characterised by %RSD of less than 5%. The limits of detection and quantification were 3x10-4 μg∙mℓ−1 and 9x10-4 μg∙mℓ−1, respectively. The accuracy of the method was validated by analysing a custom solution of certified reference material (SEP-3) and the concentration of Ni(II) obtained was in close agreement with the certified one. The Ni(II)-DMG IIP was successfully employed to trap Ni(II) ions from a matrix of sea, river and sewage water. It is believed that the Ni(II)-DMG IIP has potential to be used as sorbent material for pre-concentration of Ni(II) ions from aqueous solutions by solid-phase extraction.
- Full Text:
- Date Issued: 2011
The development of catalytic oxovanadium(IV)-containing microspheres for the oxidation of various organosulfur compounds
- Ogunlaja, Adeniyi S, Khene, M Samson, Antunes, Edith M, Nyokong, Tebello, Torto, Nelson, Tshentu, Zenixole R
- Authors: Ogunlaja, Adeniyi S , Khene, M Samson , Antunes, Edith M , Nyokong, Tebello , Torto, Nelson , Tshentu, Zenixole R
- Language: English
- Type: Article
- Identifier: vital:7324 , http://hdl.handle.net/10962/d1020574
- Description: The development of poly[allylSB-co-EGDMA] beads containing a tetradentate ligand was achieved via suspension polymerization. The catalyst poly[allylSB-co-EGDMA]-VO was synthesized by reacting VIVOSO4 with poly[allylSB-co-EGDMA]. XPS and EPR were used to confirm the presence of vanadium (V4+) on the beads. The synthesized catalyst (poly[allylSB-co-EGDMA]-VO) was found to have a BET surface area of 22 m2 g−1 and porosity of 135 Å, with the atomic force microscopy (AFM) showing more insight on the porous nature of the beads. Oxidation of thiophene (TH), benzothiophene (BT), dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT) was carried out using tert-butyl hydroperoxide (t-BuOOH) as oxidant. An overall conversion of 60%, 82%, 98% and 87% was achieved for thiophene (TH), benzothiophene (BT), dibenzothiophene (DBT) and 4,6 dimethyldibenzothiophene (4,6-DMDBT) respectively at higher (t-BuOOH) to substrate ratio and at a temperature of 40 °C. The efficient oxidation of the various organosulfur compounds presents potential for the possible application of this catalyst in oxidative desulfurization (ODS) of crude oil. , Original publication is available at http://dx.doi.org/10.1016/j.apcata.2013.05.004
- Full Text: false
- Authors: Ogunlaja, Adeniyi S , Khene, M Samson , Antunes, Edith M , Nyokong, Tebello , Torto, Nelson , Tshentu, Zenixole R
- Language: English
- Type: Article
- Identifier: vital:7324 , http://hdl.handle.net/10962/d1020574
- Description: The development of poly[allylSB-co-EGDMA] beads containing a tetradentate ligand was achieved via suspension polymerization. The catalyst poly[allylSB-co-EGDMA]-VO was synthesized by reacting VIVOSO4 with poly[allylSB-co-EGDMA]. XPS and EPR were used to confirm the presence of vanadium (V4+) on the beads. The synthesized catalyst (poly[allylSB-co-EGDMA]-VO) was found to have a BET surface area of 22 m2 g−1 and porosity of 135 Å, with the atomic force microscopy (AFM) showing more insight on the porous nature of the beads. Oxidation of thiophene (TH), benzothiophene (BT), dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT) was carried out using tert-butyl hydroperoxide (t-BuOOH) as oxidant. An overall conversion of 60%, 82%, 98% and 87% was achieved for thiophene (TH), benzothiophene (BT), dibenzothiophene (DBT) and 4,6 dimethyldibenzothiophene (4,6-DMDBT) respectively at higher (t-BuOOH) to substrate ratio and at a temperature of 40 °C. The efficient oxidation of the various organosulfur compounds presents potential for the possible application of this catalyst in oxidative desulfurization (ODS) of crude oil. , Original publication is available at http://dx.doi.org/10.1016/j.apcata.2013.05.004
- Full Text: false
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