Electrochemistry and photophysicochemical studies of titanium, tantalum and vanadium phthalocyanines in the presence of nanomaterials
- Authors: Chauke, Vongani Portia
- Date: 2012
- Subjects: Phthalocyanines -- Synthesis Electrochemistry Titanium Tantalum Vanadium
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4313 , http://hdl.handle.net/10962/d1004971
- Description: The syntheses of tetra- and octa-substituted phthalocyanine complexes of titanium (IV) oxide vanadium (IV) oxide and tantalum (V) hydroxide and their electrochemical characterisation are presented in this work. The structures and purity of these complexes were confirmed by NMR, infrared and mass spectroscopies and elemental analysis. They show good solubility in most common solvents especially non-viscous solvents such as dichloromethane and chloroform. The cyclic voltammograms (CV) showed reversible to quasi reversible behavior for all the reduction couples and the oxidation peaks were irreversible. Spectroelectrochemistry of the complexes confirmed metal and ring redox processes for TaPc and TiPc derivatives and ring based processes only for VPc complexes. The synthesis of gold nanoparticles and their conjugation with the new phthalocyanines was carried out. Similarly, single walled carbon nanotubes were conjugated to selected tantalum complexes and the characterization of all the nanomaterials and their conjugates using different techniques that include TEM, XRD and AFM is also presented in this work. The photophysical and photochemical properties and photocatalytic oxidation of cyclohexene properties of the newly synthesised in the presence of gold nanoparticles were investigated. The compounds were stable, well within the stability range for phthalocyanines. The singlet oxygen quantum yield values increased drastically in the presence of gold nanoparticles. The photocatalytic products obtained from the reaction were cyclohexene oxide, 2-cyclohexen-1-ol, 2-cyclohexene-1-one and 1,4-cyclohexanediol. The percentage conversion values, yields and selectivity values improved significantly in the presence of AuNPs. Singlet oxygen was determined to be the main agent involved in the photocatalytic oxidation of cyclohexene. The electrocatalytic oxidation of bisphenol A and p-nitrophenol was carried out using nickel tetraamino phthalocyanine and all the newly synthesised metallophthalocyanine in the presence of gold nanoparticles and single walled carbon nanotubes. The charge transfer behaviour of AuNPs was enhanced in the presence of TaPc, TiPc and VPc complexes. The presence of single walled carbon nanotubes further improved electron transfer and minimised electrode passivation.
- Full Text:
- Authors: Chauke, Vongani Portia
- Date: 2012
- Subjects: Phthalocyanines -- Synthesis Electrochemistry Titanium Tantalum Vanadium
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4313 , http://hdl.handle.net/10962/d1004971
- Description: The syntheses of tetra- and octa-substituted phthalocyanine complexes of titanium (IV) oxide vanadium (IV) oxide and tantalum (V) hydroxide and their electrochemical characterisation are presented in this work. The structures and purity of these complexes were confirmed by NMR, infrared and mass spectroscopies and elemental analysis. They show good solubility in most common solvents especially non-viscous solvents such as dichloromethane and chloroform. The cyclic voltammograms (CV) showed reversible to quasi reversible behavior for all the reduction couples and the oxidation peaks were irreversible. Spectroelectrochemistry of the complexes confirmed metal and ring redox processes for TaPc and TiPc derivatives and ring based processes only for VPc complexes. The synthesis of gold nanoparticles and their conjugation with the new phthalocyanines was carried out. Similarly, single walled carbon nanotubes were conjugated to selected tantalum complexes and the characterization of all the nanomaterials and their conjugates using different techniques that include TEM, XRD and AFM is also presented in this work. The photophysical and photochemical properties and photocatalytic oxidation of cyclohexene properties of the newly synthesised in the presence of gold nanoparticles were investigated. The compounds were stable, well within the stability range for phthalocyanines. The singlet oxygen quantum yield values increased drastically in the presence of gold nanoparticles. The photocatalytic products obtained from the reaction were cyclohexene oxide, 2-cyclohexen-1-ol, 2-cyclohexene-1-one and 1,4-cyclohexanediol. The percentage conversion values, yields and selectivity values improved significantly in the presence of AuNPs. Singlet oxygen was determined to be the main agent involved in the photocatalytic oxidation of cyclohexene. The electrocatalytic oxidation of bisphenol A and p-nitrophenol was carried out using nickel tetraamino phthalocyanine and all the newly synthesised metallophthalocyanine in the presence of gold nanoparticles and single walled carbon nanotubes. The charge transfer behaviour of AuNPs was enhanced in the presence of TaPc, TiPc and VPc complexes. The presence of single walled carbon nanotubes further improved electron transfer and minimised electrode passivation.
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Synthesis, photochemical and photophysical properties of gallium and indium phthalocyanine derivatives
- Authors: Chauke, Vongani Portia
- Date: 2008
- Subjects: Phthalocyanines , Photochemotherapy , Electrochemistry , Gallium , Indium
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4375 , http://hdl.handle.net/10962/d1005040 , Phthalocyanines , Photochemotherapy , Electrochemistry , Gallium , Indium
- Description: The syntheses of octasubstituted and unsusbstitituted Gallium(III) chloride and indium(III) chloride phthalocyanines (GaPc and InPc), their photophysical, photochemical and nonlinear optical parameters are hereby presented. The photocatalytic oxidation of 1-hexene using the synthesized GaPc and InPc complexes as well as electrochemical characterization is also presented in this thesis. Fluorescence quantum yields do not vary much among the four Ga complexes, except for complex 21c; therefore it was concluded that the effect of substituents is not significant among them. Solvents however, had an effect on the results. Lower Φ[subscript F] values were obtained in low viscosity solvents like toluene, relative to highly viscous solvents, such as DMSO. The triplet quantum yields were found to be lower in DMSO than in DMF and toluene. The rate constants for fluorescence, intersystem crossing and internal conversion as well as fluorescence and triplet lifetimes are reported. Photodegradation and singlet oxygen quantum yields have also been reported. There was no clear correlation between the latter parameters. It was however established that the four gallium MPcs were stable, within the allowed stability range for phthalocyanines. High quantum yields of triplet state (Φ[subscript T] ranging from 0.70 to 0.91 in dimethysulfoxide, DMSO) and singlet oxygen generation (Φ[subscript greek capital letter delta], ranging from 0.61 to 0.79 in DMSO) were obtained. Short triplet lifetimes 50 to 60 μs were obtained in DMSO). Calculated non-linear parameters of these complexes are compared with those of the corresponding GaPc derivatives and tetrasubstituted GaPc and InPc complexes. The optical limiting threshold intensity (I[subscript lim]) values for the InPc and GaPc derivatives were calculated and compared with those of corresponding tetrasubstituted InPc and GaPc complexes. The octasubstituted were found to be better optical limiters. Photocatalytic oxidation of 1-hexene by GaPc (21a-c) and InPc (22a-c) derivatives is also presented. The photocatalytic oxidation products for 1-hexene were 1,2- epoxyhexane and 1-hexen-3-ol. The % conversion values of 1-hexene and % selectivity of 1,2-epoxyhexane were generally higher for InPc derivatives. Even though InPc derivatives showed better photocatalytic results than GaPc derivatives, the former were less stable relative to the latter. Both type I and type II mechanism were implicated in the photocatalysis mechanism.
- Full Text:
- Authors: Chauke, Vongani Portia
- Date: 2008
- Subjects: Phthalocyanines , Photochemotherapy , Electrochemistry , Gallium , Indium
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4375 , http://hdl.handle.net/10962/d1005040 , Phthalocyanines , Photochemotherapy , Electrochemistry , Gallium , Indium
- Description: The syntheses of octasubstituted and unsusbstitituted Gallium(III) chloride and indium(III) chloride phthalocyanines (GaPc and InPc), their photophysical, photochemical and nonlinear optical parameters are hereby presented. The photocatalytic oxidation of 1-hexene using the synthesized GaPc and InPc complexes as well as electrochemical characterization is also presented in this thesis. Fluorescence quantum yields do not vary much among the four Ga complexes, except for complex 21c; therefore it was concluded that the effect of substituents is not significant among them. Solvents however, had an effect on the results. Lower Φ[subscript F] values were obtained in low viscosity solvents like toluene, relative to highly viscous solvents, such as DMSO. The triplet quantum yields were found to be lower in DMSO than in DMF and toluene. The rate constants for fluorescence, intersystem crossing and internal conversion as well as fluorescence and triplet lifetimes are reported. Photodegradation and singlet oxygen quantum yields have also been reported. There was no clear correlation between the latter parameters. It was however established that the four gallium MPcs were stable, within the allowed stability range for phthalocyanines. High quantum yields of triplet state (Φ[subscript T] ranging from 0.70 to 0.91 in dimethysulfoxide, DMSO) and singlet oxygen generation (Φ[subscript greek capital letter delta], ranging from 0.61 to 0.79 in DMSO) were obtained. Short triplet lifetimes 50 to 60 μs were obtained in DMSO). Calculated non-linear parameters of these complexes are compared with those of the corresponding GaPc derivatives and tetrasubstituted GaPc and InPc complexes. The optical limiting threshold intensity (I[subscript lim]) values for the InPc and GaPc derivatives were calculated and compared with those of corresponding tetrasubstituted InPc and GaPc complexes. The octasubstituted were found to be better optical limiters. Photocatalytic oxidation of 1-hexene by GaPc (21a-c) and InPc (22a-c) derivatives is also presented. The photocatalytic oxidation products for 1-hexene were 1,2- epoxyhexane and 1-hexen-3-ol. The % conversion values of 1-hexene and % selectivity of 1,2-epoxyhexane were generally higher for InPc derivatives. Even though InPc derivatives showed better photocatalytic results than GaPc derivatives, the former were less stable relative to the latter. Both type I and type II mechanism were implicated in the photocatalysis mechanism.
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