Phthalocyanine-nanoparticle conjugates supported on inorganic nanofibers as photocatalysts for the treatment of biological and organic pollutants as well as for hydrogen generation
- Authors: Mapukata, Sivuyisiwe
- Date: 2021-10-29
- Subjects: Phthalocyanines , Nanofibers , Nanoparticles , Zinc , Hydrogen , Organic water pollutants , Water Purification , Electrospinning , Photocatalysis , Photodegradation , Anti-infective agents
- Language: English
- Type: Doctoral theses , text
- Identifier: http://hdl.handle.net/10962/192831 , vital:45268 , 10.21504/10962/192831
- Description: This thesis reports on the synthesis, photophysicochemical and photocatalytic properties of various zinc phthalocyanines (Pcs). For enhanced properties and catalyst support, the reported Pcs were conjugated to different nanoparticles (NPs) through chemisorption as well as amide bond formation to yield Pc-NP conjugates. For increased catalyst surface area and catalyst reusability, the Pcs and some of their conjugates were also supported on electrospun inorganic nanofibers i.e. SiO2, hematite (abbreviated Hem and has formula α-Fe2O3), ZnO and TiO2 nanofibers. The effect that the number of charges on a Pc has on its antimicrobial activities was evaluated by comparing the photoactivities of neutral, octacationic and hexadecacationic Pcs against S. aureus, E. coli and C. albicans. The extent of enhancement of their antimicrobial activities upon conjugation (through chemisorption) to Ag NPs was also studied in solution and when supported on SiO2 nanofibers. The results showed that the hexadecacationic complex 3 possessed the best antimicrobial activity against all three microorganisms, in solution and when supported on the SiO2 nanofibers. Covalent conjugation of Pcs with carboxylic acid moieties (complexes 4-6) to amine functionalised NPs (Cys-Ag, NH2-Fe3O4 and Cys-Fe3O4@Ag) resulted in enhanced singlet oxygen generation and thus antibacterial efficiencies. Comparison of the photodegradation efficiencies of semiconductor nanofibers (hematite, ZnO and TiO2) when bare and when modified with a Pc (complex 6) were evaluated. Modification of the nanofibers with the Pc resulted in enhanced photoactivities for the nanofibers with the hematite nanofibers being the best. Modification of the hematite nanofibers with two different Pcs i.e. monosubstituted (complex 5) and an asymmetrical tetrasubstituted Pc (complex 6) showed that complex 6 better enhanced the activity of the nanofibers. Evaluation of the hydrogen generation efficiencies of the bare and modified TiO2 nanofibers calcined at different temperatures demonstrated that the anatase nanofibers calcined at 500 oC possessed the best catalytic efficiency. The efficiency of the TiO2 nanofibers was enhanced in the presence of the Co and Pd NPs as well as a Pc (complex 7), with the extent of enhancement being the greatest for the nanofibers modified with the Pd NPs. The reported findings therefore demonstrate the versatility of applications of Pcs for different water purification techniques when supported on different nanomaterials. , Thesis (PhD) -- Faculty of Science, Chemistry, 2021
- Full Text:
- Date Issued: 2021-10-29
- Authors: Mapukata, Sivuyisiwe
- Date: 2021-10-29
- Subjects: Phthalocyanines , Nanofibers , Nanoparticles , Zinc , Hydrogen , Organic water pollutants , Water Purification , Electrospinning , Photocatalysis , Photodegradation , Anti-infective agents
- Language: English
- Type: Doctoral theses , text
- Identifier: http://hdl.handle.net/10962/192831 , vital:45268 , 10.21504/10962/192831
- Description: This thesis reports on the synthesis, photophysicochemical and photocatalytic properties of various zinc phthalocyanines (Pcs). For enhanced properties and catalyst support, the reported Pcs were conjugated to different nanoparticles (NPs) through chemisorption as well as amide bond formation to yield Pc-NP conjugates. For increased catalyst surface area and catalyst reusability, the Pcs and some of their conjugates were also supported on electrospun inorganic nanofibers i.e. SiO2, hematite (abbreviated Hem and has formula α-Fe2O3), ZnO and TiO2 nanofibers. The effect that the number of charges on a Pc has on its antimicrobial activities was evaluated by comparing the photoactivities of neutral, octacationic and hexadecacationic Pcs against S. aureus, E. coli and C. albicans. The extent of enhancement of their antimicrobial activities upon conjugation (through chemisorption) to Ag NPs was also studied in solution and when supported on SiO2 nanofibers. The results showed that the hexadecacationic complex 3 possessed the best antimicrobial activity against all three microorganisms, in solution and when supported on the SiO2 nanofibers. Covalent conjugation of Pcs with carboxylic acid moieties (complexes 4-6) to amine functionalised NPs (Cys-Ag, NH2-Fe3O4 and Cys-Fe3O4@Ag) resulted in enhanced singlet oxygen generation and thus antibacterial efficiencies. Comparison of the photodegradation efficiencies of semiconductor nanofibers (hematite, ZnO and TiO2) when bare and when modified with a Pc (complex 6) were evaluated. Modification of the nanofibers with the Pc resulted in enhanced photoactivities for the nanofibers with the hematite nanofibers being the best. Modification of the hematite nanofibers with two different Pcs i.e. monosubstituted (complex 5) and an asymmetrical tetrasubstituted Pc (complex 6) showed that complex 6 better enhanced the activity of the nanofibers. Evaluation of the hydrogen generation efficiencies of the bare and modified TiO2 nanofibers calcined at different temperatures demonstrated that the anatase nanofibers calcined at 500 oC possessed the best catalytic efficiency. The efficiency of the TiO2 nanofibers was enhanced in the presence of the Co and Pd NPs as well as a Pc (complex 7), with the extent of enhancement being the greatest for the nanofibers modified with the Pd NPs. The reported findings therefore demonstrate the versatility of applications of Pcs for different water purification techniques when supported on different nanomaterials. , Thesis (PhD) -- Faculty of Science, Chemistry, 2021
- Full Text:
- Date Issued: 2021-10-29
Evaluation of surface functionalized electrospun polyacrylonitrile nanofibers for heavy metal ions removal from synthetic wastewater
- Maqinana, Siphosethu Sesethu
- Authors: Maqinana, Siphosethu Sesethu
- Date: 2020-12
- Subjects: Nanofibers , Nanostructured materials
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10353/20871 , vital:46680
- Description: Heavy metal ions are elements that are discharged into water streams from municipal or industrial waste. In abundance, they can be threating to the environment and human health. Amongst other several convention methods, adsorption has been proven to be the most effective method in the removal of heavy metal ions from wastewater. The aim of this research was to fabricate electrospun polyacrylonitrile (PAN) nanofibers and modify their surface to improve the adsorption efficiency for Chromium and Cadmium metal ions from synthetic wastewater. Electrospun nanofibers PAN nanofibers were fabricated via electrospinning process though careful monitoring of its parameters and modified via two-step process: hydrolysis with sodium hydroxide (NaOH), hydrochloric acid (HCl) and ethylenediamine (EDA). The morphologies, functional groups, thermal stability, chemical composition and crystallinities or amorphous structures of the nanofibers were characterised by Scanning electron microscopy (SEM), Fourier-Transform Infrared spectroscopy (FTIR), Thermogravimetric analysis (TGA), Energy dispersive X-ray analysis (EDX) and X-ray diffraction (XRD), respectively. The experiments were conducted in batch tests to analyse the effect to pH, contact time and initial concentration of the solution. Ultraviolet-Visible spectroscopy (UV-Vis) was used to analyse the concentration of metal ions. The adsorption equilibrium was reached after 120 min with a maximum adsorption capacity of 301.1 mg/g for Cd(II) ions and 195.02 mg/g for Cr(VI) ions. The adsorption capacity increased with increasing pH and initial concentration of the solution. The adsorption capacity of Cd(II) and Cr(VI) ions was higher at pH 8 and 10, respectively. The equilibrium data was best described using Freundlich isotherm with a maximum adsorption capacity for Cd(II) ions than Cr(VI) ions. Pseudo-second order kinetic model best fitted both heavy metal ions with R2 value of 0.99 for Cr(VI) ions and 0.67 for Cd(II) ions. Heavy metal ions were desorbed from the nanofibers after one regeneration cycle with an equilibrium concentration of 4.83 mg/L for Cr(VI) ions and 43.06 mg/L for Cd(II) ions. , Thesis (MSc) (Chemistry) -- University of Fort Hare, 2021
- Full Text:
- Date Issued: 2020-12
- Authors: Maqinana, Siphosethu Sesethu
- Date: 2020-12
- Subjects: Nanofibers , Nanostructured materials
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10353/20871 , vital:46680
- Description: Heavy metal ions are elements that are discharged into water streams from municipal or industrial waste. In abundance, they can be threating to the environment and human health. Amongst other several convention methods, adsorption has been proven to be the most effective method in the removal of heavy metal ions from wastewater. The aim of this research was to fabricate electrospun polyacrylonitrile (PAN) nanofibers and modify their surface to improve the adsorption efficiency for Chromium and Cadmium metal ions from synthetic wastewater. Electrospun nanofibers PAN nanofibers were fabricated via electrospinning process though careful monitoring of its parameters and modified via two-step process: hydrolysis with sodium hydroxide (NaOH), hydrochloric acid (HCl) and ethylenediamine (EDA). The morphologies, functional groups, thermal stability, chemical composition and crystallinities or amorphous structures of the nanofibers were characterised by Scanning electron microscopy (SEM), Fourier-Transform Infrared spectroscopy (FTIR), Thermogravimetric analysis (TGA), Energy dispersive X-ray analysis (EDX) and X-ray diffraction (XRD), respectively. The experiments were conducted in batch tests to analyse the effect to pH, contact time and initial concentration of the solution. Ultraviolet-Visible spectroscopy (UV-Vis) was used to analyse the concentration of metal ions. The adsorption equilibrium was reached after 120 min with a maximum adsorption capacity of 301.1 mg/g for Cd(II) ions and 195.02 mg/g for Cr(VI) ions. The adsorption capacity increased with increasing pH and initial concentration of the solution. The adsorption capacity of Cd(II) and Cr(VI) ions was higher at pH 8 and 10, respectively. The equilibrium data was best described using Freundlich isotherm with a maximum adsorption capacity for Cd(II) ions than Cr(VI) ions. Pseudo-second order kinetic model best fitted both heavy metal ions with R2 value of 0.99 for Cr(VI) ions and 0.67 for Cd(II) ions. Heavy metal ions were desorbed from the nanofibers after one regeneration cycle with an equilibrium concentration of 4.83 mg/L for Cr(VI) ions and 43.06 mg/L for Cd(II) ions. , Thesis (MSc) (Chemistry) -- University of Fort Hare, 2021
- Full Text:
- Date Issued: 2020-12
Photocatalysis of 4-chloro and 4-nonylphenols using novel symmetric phthalocyanines and asymmetric porphyrin supported on polyacrylonitrite nanofibres
- Authors: Jones, Benjamin Martin
- Date: 2020
- Subjects: Nanoparticles , Phthalocyanines , Electrospinning , Porphyrins , Nanofibers , Photocatalysis , Photocatalysis -- Environmental aspects
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/164770 , vital:41163
- Description: This work explores the synthesis and characterisation of novel symmetrical phthalocyanines and novel asymmetric porphyrins that have been embedded or linked respectively,and electrospun into fibres for application in the photocatalysis of environmental pollutants. The phthalocyanines contain pyrrole moieties without hetero atom linkers to maintain a rigid structure. The porphyrin contains a carboxy moiety utilized to construct an amide bond between the complex and the polymer prior to the spinning process. The new compounds were characterized by elemental analyses, proton nuclear magnetic resonance (HNMR)Fourier-transform infrared spectroscopy (FTIR), MALDI-TOF and UV-vis spectroscopy. The general trends of fluorescence, triplet and singlet oxygen quantum yields are described as well as their appropriate lifetimes. The photocatalytic activity of phthalocyanine embedded fibres were compared against those that had been dyed. Unfortunately, during the degradation process, the dyed fibres leeched compound and the studies could not be continued. It was seen that the porphyrin fibres linked to the polymer showed the most efficient photocatalytic activity against 4-cholorphenol and 4-nonylphenol due to irradiation at lower wavelengths consequently having higher frequencies and transferring more energy.
- Full Text:
- Date Issued: 2020
- Authors: Jones, Benjamin Martin
- Date: 2020
- Subjects: Nanoparticles , Phthalocyanines , Electrospinning , Porphyrins , Nanofibers , Photocatalysis , Photocatalysis -- Environmental aspects
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/164770 , vital:41163
- Description: This work explores the synthesis and characterisation of novel symmetrical phthalocyanines and novel asymmetric porphyrins that have been embedded or linked respectively,and electrospun into fibres for application in the photocatalysis of environmental pollutants. The phthalocyanines contain pyrrole moieties without hetero atom linkers to maintain a rigid structure. The porphyrin contains a carboxy moiety utilized to construct an amide bond between the complex and the polymer prior to the spinning process. The new compounds were characterized by elemental analyses, proton nuclear magnetic resonance (HNMR)Fourier-transform infrared spectroscopy (FTIR), MALDI-TOF and UV-vis spectroscopy. The general trends of fluorescence, triplet and singlet oxygen quantum yields are described as well as their appropriate lifetimes. The photocatalytic activity of phthalocyanine embedded fibres were compared against those that had been dyed. Unfortunately, during the degradation process, the dyed fibres leeched compound and the studies could not be continued. It was seen that the porphyrin fibres linked to the polymer showed the most efficient photocatalytic activity against 4-cholorphenol and 4-nonylphenol due to irradiation at lower wavelengths consequently having higher frequencies and transferring more energy.
- Full Text:
- Date Issued: 2020
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