Integrated photocatalyst adsorbents based on porphyrin anchored to activated carbon granules for water treatment
- Oyim, James, Amuhaya, Edith K, Matshitse, Refilwe, Mack, John, Nyokong, Tebello
- Authors: Oyim, James , Amuhaya, Edith K , Matshitse, Refilwe , Mack, John , Nyokong, Tebello
- Date: 2022
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/300101 , vital:57893 , xlink:href="https://doi.org/10.1016/j.cartre.2022.100191"
- Description: Integration of adsorption and photocatalysis processes can lead to several benefits in water treatment. Integrating well-known adsorbents with photocatalysts ensures that all the interesting components are preserved and helps to overcome the serious downsides of each material and technique when operated independently. In this work, we introduce a new concept of combining both absorption and photodegradation mechanisms using organic photocatalytic adsorbents for water purification. This was achieved by formulating photosensitizing hybrids based on a newly synthesized chloroindium (III) 5,10,15,20-tetrakis(4-acetamidophenyl) porphyrin (InTAAP) compound, anchored on oxygen functionalized coconut shell-based activated carbon granules supports. The fashioned integrated photocatalyst adsorbent hybrid (InTAAP(ACO)) was then studied for their adsorption and photodegradation efficiency using methylene blue dye, where InTAAP(ACO) showed excellent photocatalytic activity compared to ACO and unfunctionalized activated carbon granules (AC), with appreciably high and adsorption properties as AC and ACO.
- Full Text:
- Date Issued: 2022
- Authors: Oyim, James , Amuhaya, Edith K , Matshitse, Refilwe , Mack, John , Nyokong, Tebello
- Date: 2022
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/300101 , vital:57893 , xlink:href="https://doi.org/10.1016/j.cartre.2022.100191"
- Description: Integration of adsorption and photocatalysis processes can lead to several benefits in water treatment. Integrating well-known adsorbents with photocatalysts ensures that all the interesting components are preserved and helps to overcome the serious downsides of each material and technique when operated independently. In this work, we introduce a new concept of combining both absorption and photodegradation mechanisms using organic photocatalytic adsorbents for water purification. This was achieved by formulating photosensitizing hybrids based on a newly synthesized chloroindium (III) 5,10,15,20-tetrakis(4-acetamidophenyl) porphyrin (InTAAP) compound, anchored on oxygen functionalized coconut shell-based activated carbon granules supports. The fashioned integrated photocatalyst adsorbent hybrid (InTAAP(ACO)) was then studied for their adsorption and photodegradation efficiency using methylene blue dye, where InTAAP(ACO) showed excellent photocatalytic activity compared to ACO and unfunctionalized activated carbon granules (AC), with appreciably high and adsorption properties as AC and ACO.
- Full Text:
- Date Issued: 2022
Promotion of Catalytic Oxygen Reduction Reactions
- Wei, Yuqin, Zhao, Long, Yuan, Rui, Xue, Zhaoli, Mack, John, Chivumba, Choonzo, Nyokong, Tebello, Zhang, Jianming
- Authors: Wei, Yuqin , Zhao, Long , Yuan, Rui , Xue, Zhaoli , Mack, John , Chivumba, Choonzo , Nyokong, Tebello , Zhang, Jianming
- Date: 2022
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/300347 , vital:57919 , xlink:href="https://doi.org/10.1021/acs.inorgchem.2c01591"
- Description: Three ABAB-type cobalt meso-tetraarylporphyrins with fluorine (F-CoPor), acetic acid (AC-CoPor), and cyanoacetic acid (CN-CoPor) groups at the para-positions of phenyl rings at the 10,20-positions are synthesized and evaluated as catalysts for oxygen reduction reactions (ORRs). In density functional theory calculations, the frontier molecular orbitals of these complexes were found to be stabilized relative to model complexes with electron-withdrawing atoms or moieties on the meso-aryl rings. Electrochemical measurements suggest that electrodes with CN-CoPor (CN-CoPor/C) exhibit the most positive ORR potential values and the highest limiting current density in both acidic and alkali electrolytes, while the F-CoPor/C electrocatalyst exhibits extremely low ORR performance. The electron transfer numbers for the electrocatalysts are more than 3.0, indicating that a mixture of 2- and 4-electron transfer pathways occurs. The results demonstrate that coupling the hydrogen bonding properties and electron-withdrawing abilities through rational design of the substituent at the meso-position is an efficient way to modify the ORR performance.
- Full Text:
- Date Issued: 2022
- Authors: Wei, Yuqin , Zhao, Long , Yuan, Rui , Xue, Zhaoli , Mack, John , Chivumba, Choonzo , Nyokong, Tebello , Zhang, Jianming
- Date: 2022
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/300347 , vital:57919 , xlink:href="https://doi.org/10.1021/acs.inorgchem.2c01591"
- Description: Three ABAB-type cobalt meso-tetraarylporphyrins with fluorine (F-CoPor), acetic acid (AC-CoPor), and cyanoacetic acid (CN-CoPor) groups at the para-positions of phenyl rings at the 10,20-positions are synthesized and evaluated as catalysts for oxygen reduction reactions (ORRs). In density functional theory calculations, the frontier molecular orbitals of these complexes were found to be stabilized relative to model complexes with electron-withdrawing atoms or moieties on the meso-aryl rings. Electrochemical measurements suggest that electrodes with CN-CoPor (CN-CoPor/C) exhibit the most positive ORR potential values and the highest limiting current density in both acidic and alkali electrolytes, while the F-CoPor/C electrocatalyst exhibits extremely low ORR performance. The electron transfer numbers for the electrocatalysts are more than 3.0, indicating that a mixture of 2- and 4-electron transfer pathways occurs. The results demonstrate that coupling the hydrogen bonding properties and electron-withdrawing abilities through rational design of the substituent at the meso-position is an efficient way to modify the ORR performance.
- Full Text:
- Date Issued: 2022
Photophysical and enhanced nonlinear optical response in asymmetric benzothiazole substituted phthalocyanine covalently linked to semiconductor quantum dots
- Nwaji, Njemuwa, Dingiswayo, Somila, Mack, John, Nyokong, Tebello
- Authors: Nwaji, Njemuwa , Dingiswayo, Somila , Mack, John , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187851 , vital:44703 , xlink:href="https://doi.org/10.1016/j.saa.2018.06.098"
- Description: The synthesis of asymmetric benzothiazole substituted phthalocyanines (complexes 3 to 5) and their covalent attachment to glutathione (GSH) functionalized quantum dots (QDs) are reported in this work. Additionally, their photophysical and nonlinear optical properties were investigated. A decrease in the fluorescence quantum yield with corresponding increase in the triplet quantum yield was observed when the complexes were covalently linked to glutathione (GSH) functionalized cadmium telluride (CdTe) quantum dots. Reverse saturable absorption was found to be predominantly dominated by excited state absorption. The observed limiting threshold values range from 0.29–0.75 J/cm2.
- Full Text:
- Date Issued: 2019
- Authors: Nwaji, Njemuwa , Dingiswayo, Somila , Mack, John , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187851 , vital:44703 , xlink:href="https://doi.org/10.1016/j.saa.2018.06.098"
- Description: The synthesis of asymmetric benzothiazole substituted phthalocyanines (complexes 3 to 5) and their covalent attachment to glutathione (GSH) functionalized quantum dots (QDs) are reported in this work. Additionally, their photophysical and nonlinear optical properties were investigated. A decrease in the fluorescence quantum yield with corresponding increase in the triplet quantum yield was observed when the complexes were covalently linked to glutathione (GSH) functionalized cadmium telluride (CdTe) quantum dots. Reverse saturable absorption was found to be predominantly dominated by excited state absorption. The observed limiting threshold values range from 0.29–0.75 J/cm2.
- Full Text:
- Date Issued: 2019
Enhanced nonlinear optical response of benzothiazole substituted ball-type phthalocyanines in the presence of metallic nanoparticles
- Nwaji, Njemuwa, Mack, John, Nyokong, Tebello
- Authors: Nwaji, Njemuwa , Mack, John , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188149 , vital:44727 , xlink:href="https://doi.org/10.1016/j.optmat.2018.05.052"
- Description: The synthesis of zinc-zinc, gallium-gallium and indium-indium ball-type phthalocyanines (complexes 4, 5 and 6) and the surface assembly of the complexes onto metallic gold and silver nanoparticles are reported in this work. Furthermore, their photophysical and nonlinear optical dynamics were investigated. Decreases in the fluorescence quantum yields with a corresponding increase in the triplet quantum yields of the nanoconjugates in comparison to complexes 4, 5 and 6 alone were observed. The mechanism of strong reverse saturable absorption observed was found to be predominantly dependent on excited state absorption. The optical limiting thresholds range from 0.09 to 0.19 J/cm2. Enhanced triplet parameters and nonlinear optical responses were found when the complexes were conjugated to metallic nanoparticles.
- Full Text:
- Date Issued: 2018
- Authors: Nwaji, Njemuwa , Mack, John , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188149 , vital:44727 , xlink:href="https://doi.org/10.1016/j.optmat.2018.05.052"
- Description: The synthesis of zinc-zinc, gallium-gallium and indium-indium ball-type phthalocyanines (complexes 4, 5 and 6) and the surface assembly of the complexes onto metallic gold and silver nanoparticles are reported in this work. Furthermore, their photophysical and nonlinear optical dynamics were investigated. Decreases in the fluorescence quantum yields with a corresponding increase in the triplet quantum yields of the nanoconjugates in comparison to complexes 4, 5 and 6 alone were observed. The mechanism of strong reverse saturable absorption observed was found to be predominantly dependent on excited state absorption. The optical limiting thresholds range from 0.09 to 0.19 J/cm2. Enhanced triplet parameters and nonlinear optical responses were found when the complexes were conjugated to metallic nanoparticles.
- Full Text:
- Date Issued: 2018
Synthesis and photophysical properties of BODIPY-decorated graphene quantum dot–phthalocyanine conjugates
- Nwahara, Nnamdi, Nkhahle, Reitumetse, Ngoy, Bokolombe P, Mack, John, Nyokong, Tebello
- Authors: Nwahara, Nnamdi , Nkhahle, Reitumetse , Ngoy, Bokolombe P , Mack, John , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/233409 , vital:50088 , xlink:href="https://doi.org/10.1039/C8NJ00758F"
- Description: This work reports on the synthesis and characterisation of novel supramolecular hybrids containing BODIPY-decorated graphene quantum dots (BODIPY@GQDs) and zinc phthalocyanine. Graphene quantum dots (GQDs) were functionalized with L-glutathione (GSH) in order to assist coupling to the BODIPY dye. {2,9(10)16(17)23(24)-Tetrakis-[3-(diethylamino)phenoxy]phthalocyaninato}zinc(II) (1) was immobilized via π–π stacking interaction on the BODIPY-decorated GQDs and pristine GQDs to form the supramolecular hybrids 1-BODIPY@GQDs and 1-GQDs, respectively. The photophysical and photochemical properties of these conjugates were investigated. Energy transfer occurred from the (i) GQDs to BODIPY, (ii) GQDs to 1, and (iii) BODIPY@GQDs to 1via fluorescence resonance energy transfer (FRET). The highest FRET efficiency was observed for the BODIPY@GQDs (0.93). The introduction of the BODIPY core to the GQD structure resulted in higher triplet, and singlet oxygen quantum yields for the resultant Pc/GQD hybrid (1-BODIPY@GQDs). The zeta potential values obtained imply a high colloidal stability for the supramolecular hybrids. The results suggest that such hybrids may be applied in fields such as photodynamic therapy (PDT), where a high singlet oxygen quantum yield is desired.
- Full Text:
- Date Issued: 2018
- Authors: Nwahara, Nnamdi , Nkhahle, Reitumetse , Ngoy, Bokolombe P , Mack, John , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/233409 , vital:50088 , xlink:href="https://doi.org/10.1039/C8NJ00758F"
- Description: This work reports on the synthesis and characterisation of novel supramolecular hybrids containing BODIPY-decorated graphene quantum dots (BODIPY@GQDs) and zinc phthalocyanine. Graphene quantum dots (GQDs) were functionalized with L-glutathione (GSH) in order to assist coupling to the BODIPY dye. {2,9(10)16(17)23(24)-Tetrakis-[3-(diethylamino)phenoxy]phthalocyaninato}zinc(II) (1) was immobilized via π–π stacking interaction on the BODIPY-decorated GQDs and pristine GQDs to form the supramolecular hybrids 1-BODIPY@GQDs and 1-GQDs, respectively. The photophysical and photochemical properties of these conjugates were investigated. Energy transfer occurred from the (i) GQDs to BODIPY, (ii) GQDs to 1, and (iii) BODIPY@GQDs to 1via fluorescence resonance energy transfer (FRET). The highest FRET efficiency was observed for the BODIPY@GQDs (0.93). The introduction of the BODIPY core to the GQD structure resulted in higher triplet, and singlet oxygen quantum yields for the resultant Pc/GQD hybrid (1-BODIPY@GQDs). The zeta potential values obtained imply a high colloidal stability for the supramolecular hybrids. The results suggest that such hybrids may be applied in fields such as photodynamic therapy (PDT), where a high singlet oxygen quantum yield is desired.
- Full Text:
- Date Issued: 2018
Electronic structure and NH-tautomerism of a novel metal-free phenanthroline-annelated phthalocyanine
- Martynov, Alexander G, Mack, John, Ngoy, Bokolombe P, Nyokong, Tebello, Gorbunova, Yulia G, Tsivadze, Aslan Yu
- Authors: Martynov, Alexander G , Mack, John , Ngoy, Bokolombe P , Nyokong, Tebello , Gorbunova, Yulia G , Tsivadze, Aslan Yu
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/239643 , vital:50751 , xlink:href="https://doi.org/10.1016/j.dyepig.2017.01.072"
- Description: A novel low-symmetry A3B-type phthalocyanine annelated with a pyrazino[2,3-f]phenanthroline ring system and substituted with six solubilizing diisopropylphenoxy-groups (1) was synthesized by metalfree DBU-promoted cross-condensation of diiminoisoindolines derived from 4,5- bis(diisopropylphenoxy)phthalonitrile and pyrazino[2,3-f][1,10]phenanthroline-2,3-dicarbonitrile. The use of these particular precursors affords A3B phthalocyanine in 15% yield, while cross-condensation of the corresponding dinitriles yields only trace amounts of the target compound. Comparative studies of the A3B-type phthalocyanine and its symmetrical octa(diisopropylphenoxy)-substituted counterpart 2 reveal striking differences in the Q band regions of their UVevisible absorption (UVeVis) spectra, which could be readily rationalized through a comparison with calculated TD-DFT spectra. Since 1 can have two NH-tautomers with equivalent and non-equivalent NH-groups, and DFT calculations predict that the former tautomer is only 2.3 kcal/mol more stable than the latter one, a comprehensive analysis of 13C NMR spectra was carried out through the application of 1 He13C HMBC and HSQC techniques. It demonstrated that only the tautomer with equivalent NH-groups is present in solution.
- Full Text:
- Date Issued: 2017
- Authors: Martynov, Alexander G , Mack, John , Ngoy, Bokolombe P , Nyokong, Tebello , Gorbunova, Yulia G , Tsivadze, Aslan Yu
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/239643 , vital:50751 , xlink:href="https://doi.org/10.1016/j.dyepig.2017.01.072"
- Description: A novel low-symmetry A3B-type phthalocyanine annelated with a pyrazino[2,3-f]phenanthroline ring system and substituted with six solubilizing diisopropylphenoxy-groups (1) was synthesized by metalfree DBU-promoted cross-condensation of diiminoisoindolines derived from 4,5- bis(diisopropylphenoxy)phthalonitrile and pyrazino[2,3-f][1,10]phenanthroline-2,3-dicarbonitrile. The use of these particular precursors affords A3B phthalocyanine in 15% yield, while cross-condensation of the corresponding dinitriles yields only trace amounts of the target compound. Comparative studies of the A3B-type phthalocyanine and its symmetrical octa(diisopropylphenoxy)-substituted counterpart 2 reveal striking differences in the Q band regions of their UVevisible absorption (UVeVis) spectra, which could be readily rationalized through a comparison with calculated TD-DFT spectra. Since 1 can have two NH-tautomers with equivalent and non-equivalent NH-groups, and DFT calculations predict that the former tautomer is only 2.3 kcal/mol more stable than the latter one, a comprehensive analysis of 13C NMR spectra was carried out through the application of 1 He13C HMBC and HSQC techniques. It demonstrated that only the tautomer with equivalent NH-groups is present in solution.
- Full Text:
- Date Issued: 2017
Facile synthesis, spectroscopic and electrochemical properties, and theoretical calculations of porphyrin dimers with a bridging amide-bonded xanthene moiety
- Liang, Xu, Xu, Li, Li, Minzhi, Mack, John, Stone, Justin, Nyokong, Tebello, Jiang, Yu, Kobayashi, Nagao, Zhu, Weihua
- Authors: Liang, Xu , Xu, Li , Li, Minzhi , Mack, John , Stone, Justin , Nyokong, Tebello , Jiang, Yu , Kobayashi, Nagao , Zhu, Weihua
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241390 , vital:50935 , xlink:href="https://doi.org/10.1142/S1088424615500492"
- Description: A free base porphyrin dimer bridged by a flexible amide-bonded xanthene moiety and its binuclear zinc(II) complex zinc(II) complex were synthesized and characterized. Structural characterization by MS and 1H NMR spectroscopy confirmed the bridged porphyrin dimer structure. The properties of the dimers were characterized by IR, UV-visible absorption, fluorescence and magnetic circular dichroism (MCD) spectroscopy, and electrochemistry studies. Theoretical calculations were carried out to analyze the electronic structures of porphyrin dimers with a bridging amide-bonded xanthene moiety.
- Full Text:
- Date Issued: 2015
- Authors: Liang, Xu , Xu, Li , Li, Minzhi , Mack, John , Stone, Justin , Nyokong, Tebello , Jiang, Yu , Kobayashi, Nagao , Zhu, Weihua
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241390 , vital:50935 , xlink:href="https://doi.org/10.1142/S1088424615500492"
- Description: A free base porphyrin dimer bridged by a flexible amide-bonded xanthene moiety and its binuclear zinc(II) complex zinc(II) complex were synthesized and characterized. Structural characterization by MS and 1H NMR spectroscopy confirmed the bridged porphyrin dimer structure. The properties of the dimers were characterized by IR, UV-visible absorption, fluorescence and magnetic circular dichroism (MCD) spectroscopy, and electrochemistry studies. Theoretical calculations were carried out to analyze the electronic structures of porphyrin dimers with a bridging amide-bonded xanthene moiety.
- Full Text:
- Date Issued: 2015
Effect of peripheral fused ring substitution on the optical spectroscopy and electronic structure of metal phthalocyanine complexes
- Chidawanyika, Wadzanai J U, Mack, John, Shimizu, Soji, Kobayashi, Nagao, Nyokong, Tebello
- Authors: Chidawanyika, Wadzanai J U , Mack, John , Shimizu, Soji , Kobayashi, Nagao , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/263353 , vital:53620 , xlink:href="https://doi.org/10.1142/S1088424609001339"
- Description: In this paper the impact of peripheral substitution with a strongly withdrawing fused ring group on the optical spectroscopy of a metal phthalocyanine complex is analyzed. We report the synthesis of [9 (or 10), 16 (or 17), 23 (or 24)-tri-tert-butylimidophthalocyaninato]zinc(II) (ZnttbIPc), which should eventually prove to be a useful precursor for forming dimeric compounds. The electronic structure is analyzed through a detailed analysis of the UV-visible absorption and magnetic circular dichroism spectra and time-dependent density functional theory calculations. Other than a marked splitting of the Q band, the spectrum is broadly similar to that of ZnPc in terms of the main π → π* electronic bands. The vibrational bands differ markedly in the Q band region when an imido group is added to ligand periphery, relative to what is observed in the case of zinc mononaphthotribenzotetraazaporphyrin (Zn3B1N) with an additional fused benzene ring. The absorption and emission spectra lack mirror symmetry as is the case with ZnPc and thus provide possible evidence for a second set of electronic origins in the Q band region arising from n → π* rather then π → π* transitions.
- Full Text:
- Date Issued: 2009
- Authors: Chidawanyika, Wadzanai J U , Mack, John , Shimizu, Soji , Kobayashi, Nagao , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/263353 , vital:53620 , xlink:href="https://doi.org/10.1142/S1088424609001339"
- Description: In this paper the impact of peripheral substitution with a strongly withdrawing fused ring group on the optical spectroscopy of a metal phthalocyanine complex is analyzed. We report the synthesis of [9 (or 10), 16 (or 17), 23 (or 24)-tri-tert-butylimidophthalocyaninato]zinc(II) (ZnttbIPc), which should eventually prove to be a useful precursor for forming dimeric compounds. The electronic structure is analyzed through a detailed analysis of the UV-visible absorption and magnetic circular dichroism spectra and time-dependent density functional theory calculations. Other than a marked splitting of the Q band, the spectrum is broadly similar to that of ZnPc in terms of the main π → π* electronic bands. The vibrational bands differ markedly in the Q band region when an imido group is added to ligand periphery, relative to what is observed in the case of zinc mononaphthotribenzotetraazaporphyrin (Zn3B1N) with an additional fused benzene ring. The absorption and emission spectra lack mirror symmetry as is the case with ZnPc and thus provide possible evidence for a second set of electronic origins in the Q band region arising from n → π* rather then π → π* transitions.
- Full Text:
- Date Issued: 2009
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