Enhancement of the electrocatalytic activity of phthalocyanines through the reduction in symmetry and conjugation to detonation nanodiamonds
- Authors: Ncwane, Lunathi
- Date: 2023-10-13
- Subjects: Phthalocyanines , Electrocatalysis , Nanodiamonds , Hydrazine
- Language: English
- Type: Academic theses , Master's theses , text
- Identifier: http://hdl.handle.net/10962/424541 , vital:72162
- Description: This thesis reports on the synthesis of novel phthalocynines tetrakis[(benzo[d]thiazol-2ylthio)phthalocyaninato]cobalt(II)chloride (complex 1) and tris(2-(ethylthio)benzo[d]thiazole)2-(phthalocyanine-9-ylthio)propionate cobalt(II) chloride (complex 2). The complexes are combined with DNDs via different techniques such as π-π stacking, covalent linkage and sequential modification on glassy carbon electrode. The synthesized MPcs and conjugates were characterized using UV-visible, mass, Fourier transform infrared, and Raman spectroscopies as well as transmission electron microscopy and dynamic light scattering. Combining MPcs with DNDs sought to improve electrooxidation of hydrazine. The electrochemical studies were conducted using cyclic voltammetry, chronocoloumetry, electrochemical impedance spectroscopy and chronoamperometry. Hydrazine was utilized as an analyte of interest, due to its mutagenic and carcinogenic effects. Glassy carbon electrodes (GCE) were modified using drop and dry method. The conjugation via covalent linkage proved to be the best way of enhancing electrocatalytic properties. Since it performed better in terms of limit of detection (0.33 μM), even though catalytic rate and sensitivity are not the highest. , Thesis (MSc) -- Faculty of Science, Chemistry, 2023
- Full Text:
- Date Issued: 2023-10-13
- Authors: Ncwane, Lunathi
- Date: 2023-10-13
- Subjects: Phthalocyanines , Electrocatalysis , Nanodiamonds , Hydrazine
- Language: English
- Type: Academic theses , Master's theses , text
- Identifier: http://hdl.handle.net/10962/424541 , vital:72162
- Description: This thesis reports on the synthesis of novel phthalocynines tetrakis[(benzo[d]thiazol-2ylthio)phthalocyaninato]cobalt(II)chloride (complex 1) and tris(2-(ethylthio)benzo[d]thiazole)2-(phthalocyanine-9-ylthio)propionate cobalt(II) chloride (complex 2). The complexes are combined with DNDs via different techniques such as π-π stacking, covalent linkage and sequential modification on glassy carbon electrode. The synthesized MPcs and conjugates were characterized using UV-visible, mass, Fourier transform infrared, and Raman spectroscopies as well as transmission electron microscopy and dynamic light scattering. Combining MPcs with DNDs sought to improve electrooxidation of hydrazine. The electrochemical studies were conducted using cyclic voltammetry, chronocoloumetry, electrochemical impedance spectroscopy and chronoamperometry. Hydrazine was utilized as an analyte of interest, due to its mutagenic and carcinogenic effects. Glassy carbon electrodes (GCE) were modified using drop and dry method. The conjugation via covalent linkage proved to be the best way of enhancing electrocatalytic properties. Since it performed better in terms of limit of detection (0.33 μM), even though catalytic rate and sensitivity are not the highest. , Thesis (MSc) -- Faculty of Science, Chemistry, 2023
- Full Text:
- Date Issued: 2023-10-13
Enhancing the electrocatalytic activity of phthalocyanines through finding the ideal combination of substituents in push-pull phthalocyanine-based systems
- Nkhahle, Reitumetse Precious
- Authors: Nkhahle, Reitumetse Precious
- Date: 2023-10-13
- Subjects: Phthalocyanines , Electrocatalysis , Hydrazine , Nitrites , Activating group , Deactivating group
- Language: English
- Type: Academic theses , Doctoral theses , text
- Identifier: http://hdl.handle.net/10962/432578 , vital:72882 , DOI 10.21504/10962/432578
- Description: Phthalocyanines (Pcs) are a class of synthetic pigments with a similar structure to porphyrins. The work presented in this thesis is centred around these electron-rich macrocycles and their use in electrocatalysis. This body of work provides a more rigorous analysis on asymmetric Pcs, focusing on finding the “ideal” combination of substituents in the synthesis of A3B-type Pcs and how these asymmetric structures compare with their symmetric counterparts (A4) in the electrocatalysis of hydrazine and nitrite. The choice in substituents in the syntheses of the Pcs was such that there is both electron-donating and electron-withdrawing groups to induce a push-pull effect. In the studies involving the electrocatalysis of hydrazine, asymmetric cobalt Pcs (CoPcs) possessing alkyl groups as the primary substituents, with variations in the acid-containing group, along with their symmetric counterparts, probes with potential for further improvement were identified. Using voltammetric and amperometric techniques, the analyte-electrode kinetics, mechanism in which the electrochemical reaction proceeds along with the limits of detection (LoD) were determined. In the general sense, the pentadecylphenoxy-derived CoPcs performed better than those containing the tert-butyl substituent as the dominant substituent with the asymmetric CoPcs producing more favourable results than their symmetric analogues. With respect to the probes designed for nitrite, a multi-dimensional approach was undertaken in that acetaminophen was chosen as the primary substituent whilst multiple changes in the asymmetric component were made. In addition to varying the carboxylic acid-containing substituent, alkyne- and amine-based substituents were also explored in which the alkyne-containing Pc was anchored onto the electrode surface through click chemistry while the amine-bearing Pc was covalently linked (and π-stacked) to nitrogen-doped graphene quantum dots (NGQDs). Another component that was altered was the central metal where CoPcs were compared to manganese Pcs (MnPcs). The most desirable peak oxidation potential for nitrite was observed in the MnPcs as it was the lowest with adsorption sometimes being a better suited method of electrode modification relative to clicking. The inclusion of NGQDs was found to be beneficial when combined with the symmetric CoPc whilst in the presence of an asymmetric Pc complex, less desirable results were observed. Overall, there were variations in the results with the symmetric CoPc sometimes being better than some of the asymmetric CoPcs demonstrating that a blanket-approach in terms of synthesizing and applying asymmetric Pcs is not always viable. , Thesis (PhD) -- Faculty of Science, Chemistry, 2023
- Full Text:
- Date Issued: 2023-10-13
- Authors: Nkhahle, Reitumetse Precious
- Date: 2023-10-13
- Subjects: Phthalocyanines , Electrocatalysis , Hydrazine , Nitrites , Activating group , Deactivating group
- Language: English
- Type: Academic theses , Doctoral theses , text
- Identifier: http://hdl.handle.net/10962/432578 , vital:72882 , DOI 10.21504/10962/432578
- Description: Phthalocyanines (Pcs) are a class of synthetic pigments with a similar structure to porphyrins. The work presented in this thesis is centred around these electron-rich macrocycles and their use in electrocatalysis. This body of work provides a more rigorous analysis on asymmetric Pcs, focusing on finding the “ideal” combination of substituents in the synthesis of A3B-type Pcs and how these asymmetric structures compare with their symmetric counterparts (A4) in the electrocatalysis of hydrazine and nitrite. The choice in substituents in the syntheses of the Pcs was such that there is both electron-donating and electron-withdrawing groups to induce a push-pull effect. In the studies involving the electrocatalysis of hydrazine, asymmetric cobalt Pcs (CoPcs) possessing alkyl groups as the primary substituents, with variations in the acid-containing group, along with their symmetric counterparts, probes with potential for further improvement were identified. Using voltammetric and amperometric techniques, the analyte-electrode kinetics, mechanism in which the electrochemical reaction proceeds along with the limits of detection (LoD) were determined. In the general sense, the pentadecylphenoxy-derived CoPcs performed better than those containing the tert-butyl substituent as the dominant substituent with the asymmetric CoPcs producing more favourable results than their symmetric analogues. With respect to the probes designed for nitrite, a multi-dimensional approach was undertaken in that acetaminophen was chosen as the primary substituent whilst multiple changes in the asymmetric component were made. In addition to varying the carboxylic acid-containing substituent, alkyne- and amine-based substituents were also explored in which the alkyne-containing Pc was anchored onto the electrode surface through click chemistry while the amine-bearing Pc was covalently linked (and π-stacked) to nitrogen-doped graphene quantum dots (NGQDs). Another component that was altered was the central metal where CoPcs were compared to manganese Pcs (MnPcs). The most desirable peak oxidation potential for nitrite was observed in the MnPcs as it was the lowest with adsorption sometimes being a better suited method of electrode modification relative to clicking. The inclusion of NGQDs was found to be beneficial when combined with the symmetric CoPc whilst in the presence of an asymmetric Pc complex, less desirable results were observed. Overall, there were variations in the results with the symmetric CoPc sometimes being better than some of the asymmetric CoPcs demonstrating that a blanket-approach in terms of synthesizing and applying asymmetric Pcs is not always viable. , Thesis (PhD) -- Faculty of Science, Chemistry, 2023
- Full Text:
- Date Issued: 2023-10-13
The electrocatalytic activity of metallophthalocyanines and their conjugates with carbon nanomaterials and metal tungstate nanoparticles
- Authors: Ndebele, Nobuhle
- Date: 2023-10-13
- Subjects: Phthalocyanines , Electrocatalysis , Nitrites , Dopamine , Catechol , Detection limit
- Language: English
- Type: Academic theses , Doctoral theses , text
- Identifier: http://hdl.handle.net/10962/431934 , vital:72816 , DOI 10.21504/10962/431933
- Description: In this dissertation, seventeen phthalocyanine complexes were synthesised. Of these, only four are known and have been published. These complexes were synthesised using the conventional statistical condensation method that involves refluxing the phthalonitrile(s) (4-((1,3-bis(dimethylamino)propan-2-yl)oxy)phthalonitrile, 4-(4-carboxyphenoxy)phthalonitrile, 4-(4-acetylphenoxy)phthalonitrile, dimethyl 5-(3,4-dicyanophenoxy)-isophthalate, 4-(4-(tert-butyl)phenoxy)phthalonitrile, 5-phenoxylpicolinic acid phthalonitrile 4-(4-formylphenoxy) phthalonitrile, and 4-(4-(3-oxo-3-phenylprop-1-enyl) phenoxy) phthalonitrile) with the metal salt and 1,8-diazabicyclo[5.4.0]undecane as a catalyst in a high-temperature solvent. And thereafter (when necessary), isolation and purification of the target compounds were achieved through the use of silica column chromatography. These compounds were characterised using various analytical techniques such as; ultraviolet-visible absorption, mass spectroscopy, and Fourier transform infrared spectra and elemental analysis. These techniques proved that the complexes were successfully synthesised and isolated as pure compounds. Carbon-based (graphene quantum dots and nitrogen-doped graphene quantum dots) and metal oxide (bismuth tungsten oxide and nickel tungsten oxide) nanomaterials were synthesised. Together with the purchased single-walled carbon nanotubes, these nanomaterials were conjugated to some of the MPc complexes via non-covalent (carbon-based nanomaterials) and covalent (metal oxides) linkage forming hybrid materials. These nanomaterials and hybrids were characterised using various analytical methods (ultraviolet-visible absorption, X-ray diffraction, Raman spectroscopy, thermographic analysis, and dynamic light scattering). Nanomaterials were utilised herein to determine their effect on the properties of MPc complexes and provide a synergistic effect in the hope of enhancing these properties. All complexes synthesised in this work (MPcs, nanomaterials and hybrids) were employed as electrocatalysts in electrochemical sensing. These electrocatalysts were embedded onto the glassy carbon electrode via an adsorption method known as drop-casting. The modified electrode surfaces were characterised using cyclic voltammetry, electrochemical impedance spectroscopy and scanning electrochemical microscopy to determine various electrochemical parameters. These electrocatalysts were used in the detection of either nitrite, catechol and/or dopamine. The detection limits, sensitivities, kinetics and catalytic constants were among other parameters determined for each electrocatalyst. These electrocatalysts proved to be stable electrocatalysts that could potentially be used for practical applications. The determined parameters were comparable and sometimes better than those obtained in literature. , Thesis (PhD) -- Faculty of Science, Chemistry, 2023
- Full Text:
- Date Issued: 2023-10-13
- Authors: Ndebele, Nobuhle
- Date: 2023-10-13
- Subjects: Phthalocyanines , Electrocatalysis , Nitrites , Dopamine , Catechol , Detection limit
- Language: English
- Type: Academic theses , Doctoral theses , text
- Identifier: http://hdl.handle.net/10962/431934 , vital:72816 , DOI 10.21504/10962/431933
- Description: In this dissertation, seventeen phthalocyanine complexes were synthesised. Of these, only four are known and have been published. These complexes were synthesised using the conventional statistical condensation method that involves refluxing the phthalonitrile(s) (4-((1,3-bis(dimethylamino)propan-2-yl)oxy)phthalonitrile, 4-(4-carboxyphenoxy)phthalonitrile, 4-(4-acetylphenoxy)phthalonitrile, dimethyl 5-(3,4-dicyanophenoxy)-isophthalate, 4-(4-(tert-butyl)phenoxy)phthalonitrile, 5-phenoxylpicolinic acid phthalonitrile 4-(4-formylphenoxy) phthalonitrile, and 4-(4-(3-oxo-3-phenylprop-1-enyl) phenoxy) phthalonitrile) with the metal salt and 1,8-diazabicyclo[5.4.0]undecane as a catalyst in a high-temperature solvent. And thereafter (when necessary), isolation and purification of the target compounds were achieved through the use of silica column chromatography. These compounds were characterised using various analytical techniques such as; ultraviolet-visible absorption, mass spectroscopy, and Fourier transform infrared spectra and elemental analysis. These techniques proved that the complexes were successfully synthesised and isolated as pure compounds. Carbon-based (graphene quantum dots and nitrogen-doped graphene quantum dots) and metal oxide (bismuth tungsten oxide and nickel tungsten oxide) nanomaterials were synthesised. Together with the purchased single-walled carbon nanotubes, these nanomaterials were conjugated to some of the MPc complexes via non-covalent (carbon-based nanomaterials) and covalent (metal oxides) linkage forming hybrid materials. These nanomaterials and hybrids were characterised using various analytical methods (ultraviolet-visible absorption, X-ray diffraction, Raman spectroscopy, thermographic analysis, and dynamic light scattering). Nanomaterials were utilised herein to determine their effect on the properties of MPc complexes and provide a synergistic effect in the hope of enhancing these properties. All complexes synthesised in this work (MPcs, nanomaterials and hybrids) were employed as electrocatalysts in electrochemical sensing. These electrocatalysts were embedded onto the glassy carbon electrode via an adsorption method known as drop-casting. The modified electrode surfaces were characterised using cyclic voltammetry, electrochemical impedance spectroscopy and scanning electrochemical microscopy to determine various electrochemical parameters. These electrocatalysts were used in the detection of either nitrite, catechol and/or dopamine. The detection limits, sensitivities, kinetics and catalytic constants were among other parameters determined for each electrocatalyst. These electrocatalysts proved to be stable electrocatalysts that could potentially be used for practical applications. The determined parameters were comparable and sometimes better than those obtained in literature. , Thesis (PhD) -- Faculty of Science, Chemistry, 2023
- Full Text:
- Date Issued: 2023-10-13
Electrocatalytic activity of symmetric and asymmetric Co(II) and Mn(III) porphyrins in the presence of graphene quantum dots towards the oxidation of hydrazine
- Authors: Jokazi, Mbulelo
- Date: 2022-10-14
- Subjects: Electrocatalysis , Hydrazine , Quantum dots , Graphene , Porphyrins
- Language: English
- Type: Academic theses , Master's theses , text
- Identifier: http://hdl.handle.net/10962/362894 , vital:65372
- Description: The influence of metal porphyrins in electro-oxidation of hydrazine is explored. A series of symmetric and asymmetric porphyrins alone and in the presence of graphene quantum dots (GQDs) are employed in this work. Tetra 4-aminophenyl porphyrin, manganese tetra 4-aminophenyl porphyrin, manganese tetra 4-aminophenyl porphyrin--GQDs, and manganese tetra 4-aminophenyl porphyrin@GQDs are the symmetric porphyrins. The asymmetric porphyrin and composites are 5, 10, 15-tris(aminophenyl)-20-(4-carboxyphenyl) porphyrins, manganese 5, 10, 15-tris(aminophenyl)-20-(4-carboxyphenyl) porphyrins, cobalt 5, 10, 15-tris(aminophenyl)-20-(4-carboxyphenyl) porphyrins, manganese 5, 10, 15-tris(aminophenyl)-20-(4-carboxyphenyl) porphyrins--GQDs, and cobalt 5, 10, 15-tris(aminophenyl)-20-(4-carboxyphenyl) porphyrins--GQDs. These complexes were synthesized and characterized accordingly and applied for electrocatalysis. The electrocatalytic experiments were carried out using glassy carbon electrode and the modification was through drop-dry method. The porphyrin and GQDs synthesized were characterized using UV-Vis spectroscopy, Mass spectrometry, X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy and energy dispersive x-ray spectroscopy. The modified electrodes were characterized using cyclic voltammetry and electrochemical Impedance spectroscopy. The introduction of metal ion in the center of the porphyrin improved electrocatalysis. The presence of push-pull substituents in the porphyrin lowered the oxidation potential and improved the catalysis. The presence of GQDs improved catalysis in both symmetric and asymmetric porphyrin compared to individual components. Cobalt porphyrins showed better activity than manganese porphyrin. , Thesis (MSc) -- Faculty of Science, Chemistry, 2022
- Full Text:
- Date Issued: 2022-10-14
- Authors: Jokazi, Mbulelo
- Date: 2022-10-14
- Subjects: Electrocatalysis , Hydrazine , Quantum dots , Graphene , Porphyrins
- Language: English
- Type: Academic theses , Master's theses , text
- Identifier: http://hdl.handle.net/10962/362894 , vital:65372
- Description: The influence of metal porphyrins in electro-oxidation of hydrazine is explored. A series of symmetric and asymmetric porphyrins alone and in the presence of graphene quantum dots (GQDs) are employed in this work. Tetra 4-aminophenyl porphyrin, manganese tetra 4-aminophenyl porphyrin, manganese tetra 4-aminophenyl porphyrin--GQDs, and manganese tetra 4-aminophenyl porphyrin@GQDs are the symmetric porphyrins. The asymmetric porphyrin and composites are 5, 10, 15-tris(aminophenyl)-20-(4-carboxyphenyl) porphyrins, manganese 5, 10, 15-tris(aminophenyl)-20-(4-carboxyphenyl) porphyrins, cobalt 5, 10, 15-tris(aminophenyl)-20-(4-carboxyphenyl) porphyrins, manganese 5, 10, 15-tris(aminophenyl)-20-(4-carboxyphenyl) porphyrins--GQDs, and cobalt 5, 10, 15-tris(aminophenyl)-20-(4-carboxyphenyl) porphyrins--GQDs. These complexes were synthesized and characterized accordingly and applied for electrocatalysis. The electrocatalytic experiments were carried out using glassy carbon electrode and the modification was through drop-dry method. The porphyrin and GQDs synthesized were characterized using UV-Vis spectroscopy, Mass spectrometry, X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy and energy dispersive x-ray spectroscopy. The modified electrodes were characterized using cyclic voltammetry and electrochemical Impedance spectroscopy. The introduction of metal ion in the center of the porphyrin improved electrocatalysis. The presence of push-pull substituents in the porphyrin lowered the oxidation potential and improved the catalysis. The presence of GQDs improved catalysis in both symmetric and asymmetric porphyrin compared to individual components. Cobalt porphyrins showed better activity than manganese porphyrin. , Thesis (MSc) -- Faculty of Science, Chemistry, 2022
- Full Text:
- Date Issued: 2022-10-14
Substituent effects on the electrocatalytic activity of cobalt phthalocyanine in the presence of graphene quantum dots
- Centane, Sixolile Sibongiseni
- Authors: Centane, Sixolile Sibongiseni
- Date: 2019
- Subjects: Phthalocyanines , Quantum dots , Electrocatalysis , Electrochemistry
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/67614 , vital:29121
- Description: The electrocatalytic activity of metallophthalocyanines derivatives is explored. Cobalt monocarboxyphenoxy phthalocyanine (1), cobalt tetracarboxyphenoxy phthalocyanine (2), cobalt tetraaminophenoxy phthalocyanine (3) and cobalt tris-(tert-butylphenoxy) monocarboxyphenoxy phthalocyanine (4) are the phthalocyanines employed in this work. The metallophthalocyanines were employed alone as well as in the presence of the carbon based graphene quantum dots. The electrocatalytic behaviour of functionalized GQDs is also explored herein. The catalytic processes studies were conducted on a glassy carbon electrode surface. Modification of the electrode was achieved by the adsorption method. The materials were adsorbed either alone, as premixed/covalently linked GQDs/Pc conjugates or sequentially. Sequentially adsorbed electrodes involved the phthalocyanines on top or beneath GQDs. Sequentially modified electrodes where the phthalocyanine had higher currents and low detection limits than when the phthalocyanine is underneath. Premixed conjugates showed better activity than the covalently formed conjugates. The nanomaterials synthesized and used in this work were characterized using transmission electron microscopy, UV-Vis spectroscopy, dynamic light scattering, Raman spectroscopy, X-ray diffraction, Atomic Force Microscopy and X-ray photoelectron spectroscopy. The modified electrodes were characterized using cyclic voltammetry and scanning electrochemical spectroscopy. The electrocatalytic activity of the modified electrodes towards the oxidation of hydrazine was evaluated using cyclic voltammetry and chronoamperometry. Superior catalytic activity was observed for the conjugates compared to that of the individual conjugates.
- Full Text:
- Date Issued: 2019
- Authors: Centane, Sixolile Sibongiseni
- Date: 2019
- Subjects: Phthalocyanines , Quantum dots , Electrocatalysis , Electrochemistry
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/67614 , vital:29121
- Description: The electrocatalytic activity of metallophthalocyanines derivatives is explored. Cobalt monocarboxyphenoxy phthalocyanine (1), cobalt tetracarboxyphenoxy phthalocyanine (2), cobalt tetraaminophenoxy phthalocyanine (3) and cobalt tris-(tert-butylphenoxy) monocarboxyphenoxy phthalocyanine (4) are the phthalocyanines employed in this work. The metallophthalocyanines were employed alone as well as in the presence of the carbon based graphene quantum dots. The electrocatalytic behaviour of functionalized GQDs is also explored herein. The catalytic processes studies were conducted on a glassy carbon electrode surface. Modification of the electrode was achieved by the adsorption method. The materials were adsorbed either alone, as premixed/covalently linked GQDs/Pc conjugates or sequentially. Sequentially adsorbed electrodes involved the phthalocyanines on top or beneath GQDs. Sequentially modified electrodes where the phthalocyanine had higher currents and low detection limits than when the phthalocyanine is underneath. Premixed conjugates showed better activity than the covalently formed conjugates. The nanomaterials synthesized and used in this work were characterized using transmission electron microscopy, UV-Vis spectroscopy, dynamic light scattering, Raman spectroscopy, X-ray diffraction, Atomic Force Microscopy and X-ray photoelectron spectroscopy. The modified electrodes were characterized using cyclic voltammetry and scanning electrochemical spectroscopy. The electrocatalytic activity of the modified electrodes towards the oxidation of hydrazine was evaluated using cyclic voltammetry and chronoamperometry. Superior catalytic activity was observed for the conjugates compared to that of the individual conjugates.
- Full Text:
- Date Issued: 2019
Nanocomposites of carbon nanomaterials and metallophthalocyanines : applications towards electrocatalysis
- Authors: Nyoni, Stephen
- Date: 2016
- Subjects: Nanocomposites (Materials) , Nanostructured materials , Electrocatalysis
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4561 , http://hdl.handle.net/10962/d1020846
- Description: Nanohybrid materials have been prepared and examined for their electrocatalytic activity. The nanocomposites have been prepared from carbon nanomaterials (multiwalled carbon nanotubes (MWCNTs) and graphene nanosheets), cadmium selenide quantum dots and metallophthalocyanines (MPcs). The MPcs used in this work are cobalt tetraamino-phthalocyanine (CoTAPc) and tetra (4-(4,6-diaminopyrimidin-2-ylthio) phthalocyaninatocobalt (II)) (CoPyPc). Their activity has also been explored in different forms; polymeric MPcs, iodine doped MPcs and covalently linked MPcs. The premixed drop-dry, sequential drop-dry and electropolymerisation electrode modification techniques were used to prepare nanocomposite catalysts on the glassy carbon electrode (GCE) surface. The sequential drop dry technique for MPc and MWCNTs gave better catalytic responses in terms of limit of detection, catalytic and electron transfer rate constants relative to the premixed. MWCNTs and CdSe-QDs have been used as intercalating agents to reduce restacking of graphene nanosheets during nanocomposite preparation. Voltammetry, chronoamperometry, scanning electrochemical microscopy and electrochemical impedance spectroscopy methods are used for electrochemical characterization modified GCE. X-ray photoelectron spectroscopy, X-ray diffractometry, transmission electron microscopy, scanning electron microscopy, infra-red spectroscopy, Raman spectroscopy were used to explore surface functionalities, morphology and topography of the nanocomposites. Electrocatalytic activity and possible applications of the modified electrodes were tested using oxygen reduction reaction, l-cysteine oxidation and paraquat reduction. Activity of nanocomposites was found superior over individual nanomaterials in these applications.
- Full Text:
- Date Issued: 2016
- Authors: Nyoni, Stephen
- Date: 2016
- Subjects: Nanocomposites (Materials) , Nanostructured materials , Electrocatalysis
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4561 , http://hdl.handle.net/10962/d1020846
- Description: Nanohybrid materials have been prepared and examined for their electrocatalytic activity. The nanocomposites have been prepared from carbon nanomaterials (multiwalled carbon nanotubes (MWCNTs) and graphene nanosheets), cadmium selenide quantum dots and metallophthalocyanines (MPcs). The MPcs used in this work are cobalt tetraamino-phthalocyanine (CoTAPc) and tetra (4-(4,6-diaminopyrimidin-2-ylthio) phthalocyaninatocobalt (II)) (CoPyPc). Their activity has also been explored in different forms; polymeric MPcs, iodine doped MPcs and covalently linked MPcs. The premixed drop-dry, sequential drop-dry and electropolymerisation electrode modification techniques were used to prepare nanocomposite catalysts on the glassy carbon electrode (GCE) surface. The sequential drop dry technique for MPc and MWCNTs gave better catalytic responses in terms of limit of detection, catalytic and electron transfer rate constants relative to the premixed. MWCNTs and CdSe-QDs have been used as intercalating agents to reduce restacking of graphene nanosheets during nanocomposite preparation. Voltammetry, chronoamperometry, scanning electrochemical microscopy and electrochemical impedance spectroscopy methods are used for electrochemical characterization modified GCE. X-ray photoelectron spectroscopy, X-ray diffractometry, transmission electron microscopy, scanning electron microscopy, infra-red spectroscopy, Raman spectroscopy were used to explore surface functionalities, morphology and topography of the nanocomposites. Electrocatalytic activity and possible applications of the modified electrodes were tested using oxygen reduction reaction, l-cysteine oxidation and paraquat reduction. Activity of nanocomposites was found superior over individual nanomaterials in these applications.
- Full Text:
- Date Issued: 2016
Electrode surface modification using metallophthalocyanines and metal nanoparticles : electrocatalytic activity
- Authors: Maringa, Audacity
- Date: 2015
- Subjects: Phthalocyanines , Nanoparticles , Electrocatalysis , Scanning electron microscopy , X-ray photoelectron spectroscopy , Electrochemistry , Scanning electrochemical microscopy
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4541 , http://hdl.handle.net/10962/d1017921
- Description: Metallophthalocyanines and metal nanoparticles were successfully synthesized and applied for the electrooxidation of amitrole, nitrite and hydrazine individually or when employed together. The synthesized materials were characterized using the following techniques: predominantly scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), electrochemistry and scanning electrochemical microscopy (SECM). Different electrode modification methods were used to modify the glassy carbon substrates. The methods include adsorption, electrodeposition, electropolymerization and click chemistry. Modifying the glassy carbon substrate with MPc (electropolymerization) followed by metal nanoparticles (electrodeposition) or vice versa, made a hybrid modified surface that had efficient electron transfer. This was confirmed by electrochemical impedance studies with voltammetry measurements having lower detection potentials for the analytes. This work also describes for the first time the micropatterning of the glassy carbon substrate using the SECM tip. The substrate was electrografted with 4-azidobenzenediazonium salt and then the click reaction was performed using ethynylferrocene facilitated by Cu⁺ produced at the SECM tip. The SECM imaging was then used to show the clicked spot.
- Full Text:
- Date Issued: 2015
- Authors: Maringa, Audacity
- Date: 2015
- Subjects: Phthalocyanines , Nanoparticles , Electrocatalysis , Scanning electron microscopy , X-ray photoelectron spectroscopy , Electrochemistry , Scanning electrochemical microscopy
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4541 , http://hdl.handle.net/10962/d1017921
- Description: Metallophthalocyanines and metal nanoparticles were successfully synthesized and applied for the electrooxidation of amitrole, nitrite and hydrazine individually or when employed together. The synthesized materials were characterized using the following techniques: predominantly scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), electrochemistry and scanning electrochemical microscopy (SECM). Different electrode modification methods were used to modify the glassy carbon substrates. The methods include adsorption, electrodeposition, electropolymerization and click chemistry. Modifying the glassy carbon substrate with MPc (electropolymerization) followed by metal nanoparticles (electrodeposition) or vice versa, made a hybrid modified surface that had efficient electron transfer. This was confirmed by electrochemical impedance studies with voltammetry measurements having lower detection potentials for the analytes. This work also describes for the first time the micropatterning of the glassy carbon substrate using the SECM tip. The substrate was electrografted with 4-azidobenzenediazonium salt and then the click reaction was performed using ethynylferrocene facilitated by Cu⁺ produced at the SECM tip. The SECM imaging was then used to show the clicked spot.
- Full Text:
- Date Issued: 2015
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