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
Hydrogen economy : MEA manufacturing for PEM electrolysers
- Authors: Gojela, Ntombekaya
- Date: 2011
- Subjects: Water -- Electrolysis , Hydrogen
- Language: English
- Type: Thesis , Masters , MTech
- Identifier: vital:10380 , http://hdl.handle.net/10948/1483 , Water -- Electrolysis , Hydrogen
- Description: The electrolysis of water was evaluated as a potentially efficient, as a low cost means of hydrogen production. The theoretical energy, voltage, current, and energy efficiencies of water electrolysis were considered by using various catalyst materials used in the fabrication of membrane electrode assemblies used in low temperature water electrolysis systems. Traditionally, iridium based catalysts have shown to be the most suitable material for its use on electrocatalysis of water to form hydrogen. This study showed that a combination of various elements as a binary and or ternary mixture in the base catalyst that was applied to the anode and cathode by using the Adam’s method had shown to give comparatively good results to that of using iridium oxide on its own. These catalysts were characterized by cyclic voltammetry, at different temperatures (30oC-80oC) with a range of catalyst loading of 0.2-0.5 mg.cm-2 noble metals. The study showed that the Ir40Co40 mixture as an anode catalyst was found to show highest hydrogen efficiency of 73 percent with a relatively low over potential of 0.925V at higher temperature of 80oC. The mixture also showed to give the best electrocatalytic activity with a low Tafel slope of 30.1mV.dec-1. Whereas the Ir50Pt50 showed a comparatively lower hydrogen efficiency of 65 percent with a lower over potential of 0.6V at 50oC. Ternary mixed oxide of Ir20Ru40Co40 showed an even lower over potential of 0.5- 0.6V over a large range of temperatures with a low hydrogen efficiency of 44 percent but gave good electrocatalytic activity in terms of the Tafel slope analysis. On the other hand, mixtures with relatively cheaper material such as Nickel in binary mixture systems such as Pt50Ni50 as cathode catalyst was found to show promising performance of a relatively low over potential that was less than 1.4 V with a low hydrogen efficiency of 62.1 percent Ternary cathode catalyst materials such as Pt33Ni33Co33 exhibited good performance with higher hydrogen efficiency of 65.2 percent at lower over potential of 1.2 V and a higher Tafel slope of 133.9 mV.dec-1 at 80 0C.
- Full Text:
- Date Issued: 2011
- Authors: Gojela, Ntombekaya
- Date: 2011
- Subjects: Water -- Electrolysis , Hydrogen
- Language: English
- Type: Thesis , Masters , MTech
- Identifier: vital:10380 , http://hdl.handle.net/10948/1483 , Water -- Electrolysis , Hydrogen
- Description: The electrolysis of water was evaluated as a potentially efficient, as a low cost means of hydrogen production. The theoretical energy, voltage, current, and energy efficiencies of water electrolysis were considered by using various catalyst materials used in the fabrication of membrane electrode assemblies used in low temperature water electrolysis systems. Traditionally, iridium based catalysts have shown to be the most suitable material for its use on electrocatalysis of water to form hydrogen. This study showed that a combination of various elements as a binary and or ternary mixture in the base catalyst that was applied to the anode and cathode by using the Adam’s method had shown to give comparatively good results to that of using iridium oxide on its own. These catalysts were characterized by cyclic voltammetry, at different temperatures (30oC-80oC) with a range of catalyst loading of 0.2-0.5 mg.cm-2 noble metals. The study showed that the Ir40Co40 mixture as an anode catalyst was found to show highest hydrogen efficiency of 73 percent with a relatively low over potential of 0.925V at higher temperature of 80oC. The mixture also showed to give the best electrocatalytic activity with a low Tafel slope of 30.1mV.dec-1. Whereas the Ir50Pt50 showed a comparatively lower hydrogen efficiency of 65 percent with a lower over potential of 0.6V at 50oC. Ternary mixed oxide of Ir20Ru40Co40 showed an even lower over potential of 0.5- 0.6V over a large range of temperatures with a low hydrogen efficiency of 44 percent but gave good electrocatalytic activity in terms of the Tafel slope analysis. On the other hand, mixtures with relatively cheaper material such as Nickel in binary mixture systems such as Pt50Ni50 as cathode catalyst was found to show promising performance of a relatively low over potential that was less than 1.4 V with a low hydrogen efficiency of 62.1 percent Ternary cathode catalyst materials such as Pt33Ni33Co33 exhibited good performance with higher hydrogen efficiency of 65.2 percent at lower over potential of 1.2 V and a higher Tafel slope of 133.9 mV.dec-1 at 80 0C.
- Full Text:
- Date Issued: 2011
Characterization of hydrogen and helium implanted silicon carbide
- Authors: O'Connell, Jacques Herman
- Date: 2009
- Subjects: Silicon carbide , Hydrogen , Helium
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10539 , http://hdl.handle.net/10948/979 , Silicon carbide , Hydrogen , Helium
- Description: This dissertation focuses on the characterization of hydrogen implanted 3C-SiC and helium implanted 6H-SiC and the interaction of silver and palladium with the SiC. The main technique used for the analysis of the implanted SiC was transmission electron microscopy (TEM), although scanning electron microscopy (SEM) and nanoindentation hardness testing were also used. Both H and He implantations were done at an ion energy of 100 keV and the total dose for both species was 1017 ions/cm2. Specimens were annealed at 1000 °C for 20 min in an inert atmosphere. The observed depth of ion damage agreed closely with that predicted by TRIM 2008. The damaged region in the He implanted specimens had a high density of small bubbles but no cracks were observed. Severe cracking was observed along the damaged region in the H implanted specimens. A second phase hexagonal (4H-SiC) was detected in two grains in the 3C-SiC and some grown in voids were also observed. The wettability of SiC by a 2:1 by volume mixture of Ag and Pd is extremely low but is significantly increased through the addition of Si to the mixture. The Si containing metal mixture was found to migrate along the grain boundaries of polycrystalline 3CSiC while sealing the point of entry. Pd attacks SiC and severe etching was observed on the surface of 6H-SiC. An epitaxially orientated Pd2Si inclusion was observed in the 6H-SiC. No effect of implantation damage on the interaction of Pd and Ag with SiC was observed. Pd etched the surface of the He implanted 6H-SiC down through the damaged region with no evidence of implantation damage left after 67 hours of annealing and thus no conclusions could be drawn. The metal mixture interacted with the non implanted surface of the H implanted 3C-SiC after dissolving the Si substrate and therefore the effect of the ion damage on the interaction could not be investigated. Nanoindentation hardness measurements showed a marked increase in hardness of He implanted 6H-SiC annealed for 20 min at 1000 °C over that of as implanted and virgin material. There was also a large decrease in hardness corresponding to the depth of the ion damage.
- Full Text:
- Date Issued: 2009
- Authors: O'Connell, Jacques Herman
- Date: 2009
- Subjects: Silicon carbide , Hydrogen , Helium
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10539 , http://hdl.handle.net/10948/979 , Silicon carbide , Hydrogen , Helium
- Description: This dissertation focuses on the characterization of hydrogen implanted 3C-SiC and helium implanted 6H-SiC and the interaction of silver and palladium with the SiC. The main technique used for the analysis of the implanted SiC was transmission electron microscopy (TEM), although scanning electron microscopy (SEM) and nanoindentation hardness testing were also used. Both H and He implantations were done at an ion energy of 100 keV and the total dose for both species was 1017 ions/cm2. Specimens were annealed at 1000 °C for 20 min in an inert atmosphere. The observed depth of ion damage agreed closely with that predicted by TRIM 2008. The damaged region in the He implanted specimens had a high density of small bubbles but no cracks were observed. Severe cracking was observed along the damaged region in the H implanted specimens. A second phase hexagonal (4H-SiC) was detected in two grains in the 3C-SiC and some grown in voids were also observed. The wettability of SiC by a 2:1 by volume mixture of Ag and Pd is extremely low but is significantly increased through the addition of Si to the mixture. The Si containing metal mixture was found to migrate along the grain boundaries of polycrystalline 3CSiC while sealing the point of entry. Pd attacks SiC and severe etching was observed on the surface of 6H-SiC. An epitaxially orientated Pd2Si inclusion was observed in the 6H-SiC. No effect of implantation damage on the interaction of Pd and Ag with SiC was observed. Pd etched the surface of the He implanted 6H-SiC down through the damaged region with no evidence of implantation damage left after 67 hours of annealing and thus no conclusions could be drawn. The metal mixture interacted with the non implanted surface of the H implanted 3C-SiC after dissolving the Si substrate and therefore the effect of the ion damage on the interaction could not be investigated. Nanoindentation hardness measurements showed a marked increase in hardness of He implanted 6H-SiC annealed for 20 min at 1000 °C over that of as implanted and virgin material. There was also a large decrease in hardness corresponding to the depth of the ion damage.
- Full Text:
- Date Issued: 2009
Reduction of tungsten oxides with carbon and hydrogen
- Authors: Venables, Dean Stuart
- Date: 1996
- Subjects: Oxidation-reduction reaction , Tungsten , Hydrogen , Carbon
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4342 , http://hdl.handle.net/10962/d1005004 , Oxidation-reduction reaction , Tungsten , Hydrogen , Carbon
- Description: The reductions of WO₃ with hydrogen, with CO, and with carbon, as well as the reduction of WO₃/graphite mixtures with hydrogen, were studied using thermogravimetry, evolved gas analysis, X-ray powder diffraction, and scanning electron microscopy. The intermediate phases W₂₀O₅₈, W₁₈O₄₉ and WO₂, were observed in the reductions. The final product of the reductions with hydrogen and carbon was tungsten, and we was formed in the reduction with CO. The reaction paths in the overall processes were determined. The reactant/product gas ratio had a considerable influence on which reactions took place. The morphology of the sample was characterised at different stages of the reduction. The shape of the WO₃ particles was retained during the reduction. Particle growth was observed in the reduction with hydrogen and was attributed to the formation of WO₂(OH)₂(g). The kinetics of the reductions were investigated , and the reaction mechanisms determined. The reduction of WO₃ with CO was studied from 650 to 900°C, and occurred at a phase boundary with an activation energy of 40 kJ mol⁻¹ . The reduction of WO₂, was studied under the same conditions. The reaction also occurred at a phase boundary and had an activation energy of 62 kJ mol⁻¹. The reduction of WO₃ with carbon was studied from 935 to 1100°C and took place via CO and CO₂. Two stages were observed in the reduction . The first stage, which corresponded approximately to the formation of WO₂ had an activation energy of 66 kJ mol⁻¹ and was limited by diffusion through the porous reacting particles. The second stage was first order and had an activation energy of 40 kJ mol⁻¹. The reduction of WO₃ and WO₃ graphite mixtures with hydrogen were studied from 575 to 975 °C. The reactions were controlled by mass-transfer under the conditions investigated. The addition of carbon increased the rate of the reduction process , but did not affect the phases formed in the system. CO₂ was evolved mainly at the start, and CO mainly at the end of the process.
- Full Text:
- Date Issued: 1996
- Authors: Venables, Dean Stuart
- Date: 1996
- Subjects: Oxidation-reduction reaction , Tungsten , Hydrogen , Carbon
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4342 , http://hdl.handle.net/10962/d1005004 , Oxidation-reduction reaction , Tungsten , Hydrogen , Carbon
- Description: The reductions of WO₃ with hydrogen, with CO, and with carbon, as well as the reduction of WO₃/graphite mixtures with hydrogen, were studied using thermogravimetry, evolved gas analysis, X-ray powder diffraction, and scanning electron microscopy. The intermediate phases W₂₀O₅₈, W₁₈O₄₉ and WO₂, were observed in the reductions. The final product of the reductions with hydrogen and carbon was tungsten, and we was formed in the reduction with CO. The reaction paths in the overall processes were determined. The reactant/product gas ratio had a considerable influence on which reactions took place. The morphology of the sample was characterised at different stages of the reduction. The shape of the WO₃ particles was retained during the reduction. Particle growth was observed in the reduction with hydrogen and was attributed to the formation of WO₂(OH)₂(g). The kinetics of the reductions were investigated , and the reaction mechanisms determined. The reduction of WO₃ with CO was studied from 650 to 900°C, and occurred at a phase boundary with an activation energy of 40 kJ mol⁻¹ . The reduction of WO₂, was studied under the same conditions. The reaction also occurred at a phase boundary and had an activation energy of 62 kJ mol⁻¹. The reduction of WO₃ with carbon was studied from 935 to 1100°C and took place via CO and CO₂. Two stages were observed in the reduction . The first stage, which corresponded approximately to the formation of WO₂ had an activation energy of 66 kJ mol⁻¹ and was limited by diffusion through the porous reacting particles. The second stage was first order and had an activation energy of 40 kJ mol⁻¹. The reduction of WO₃ and WO₃ graphite mixtures with hydrogen were studied from 575 to 975 °C. The reactions were controlled by mass-transfer under the conditions investigated. The addition of carbon increased the rate of the reduction process , but did not affect the phases formed in the system. CO₂ was evolved mainly at the start, and CO mainly at the end of the process.
- Full Text:
- Date Issued: 1996
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