Comparative efficiency of immobilized non-transition metal phthalocyanine photosensitizers for the visible light transformation of chlorophenols
- Agboola, Bolade, Ozoemena, Kenneth I, Nyokong, Tebello
- Authors: Agboola, Bolade , Ozoemena, Kenneth I , Nyokong, Tebello
- Date: 2006
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/286043 , vital:56233 , xlink:href="https://doi.org/10.1016/j.molcata.2005.12.009"
- Description: Photolysis of aqueous solutions of chlorophenols (4-chlorophenol, 2,4-dichlorophenol, 2,4,5-trichlorophenol and pentachlorophenol) in the presence of immobilized non-transition metal phthalocyanine photosensitizers onto Amberlite® is presented. The photosensitizers studied are: Al (AlOCPc) and Zn (ZnOCPc) octacarboxyphthalocyanines; Al (AlPcS4) and Zn (ZnPcS4) tetrasulfophthalocyanines; sulfonated phthalocyanine complexes (containing mixtures of differently substituted derivatives) of Al (AlPcSmix), Zn (ZnPcSmix), Ge (GePcSmix), Si (SiPcSmix) and Sn (SnPcSmix). Photolysis of the chlorophenols resulted mainly in the formation of chlorobenzoquinone derivatives. The complexes showed order of activity towards the transformation of pentachlorophenol as follows: ZnOCPc > SiPcSmix > SnPcSmix > ZnPcSmix > GePcSmix > ZnPcS4 > AlPcSmix > AlOCPc > AlPcS4. The generation of singlet oxygen (1O2) by these immobilized MPc photosensitizers was found to play a major role in their photoactivities towards the transformation of these chlorophenols. Langmuir–Hinshelwood (L–H) kinetic model studies showed that the ZnOCPc, GePcSmix and ZnPcSmix photocatalysis occurred on the catalysts surface. © 2005 Elsevier B.V. All rights reserved.
- Full Text:
- Authors: Agboola, Bolade , Ozoemena, Kenneth I , Nyokong, Tebello
- Date: 2006
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/286043 , vital:56233 , xlink:href="https://doi.org/10.1016/j.molcata.2005.12.009"
- Description: Photolysis of aqueous solutions of chlorophenols (4-chlorophenol, 2,4-dichlorophenol, 2,4,5-trichlorophenol and pentachlorophenol) in the presence of immobilized non-transition metal phthalocyanine photosensitizers onto Amberlite® is presented. The photosensitizers studied are: Al (AlOCPc) and Zn (ZnOCPc) octacarboxyphthalocyanines; Al (AlPcS4) and Zn (ZnPcS4) tetrasulfophthalocyanines; sulfonated phthalocyanine complexes (containing mixtures of differently substituted derivatives) of Al (AlPcSmix), Zn (ZnPcSmix), Ge (GePcSmix), Si (SiPcSmix) and Sn (SnPcSmix). Photolysis of the chlorophenols resulted mainly in the formation of chlorobenzoquinone derivatives. The complexes showed order of activity towards the transformation of pentachlorophenol as follows: ZnOCPc > SiPcSmix > SnPcSmix > ZnPcSmix > GePcSmix > ZnPcS4 > AlPcSmix > AlOCPc > AlPcS4. The generation of singlet oxygen (1O2) by these immobilized MPc photosensitizers was found to play a major role in their photoactivities towards the transformation of these chlorophenols. Langmuir–Hinshelwood (L–H) kinetic model studies showed that the ZnOCPc, GePcSmix and ZnPcSmix photocatalysis occurred on the catalysts surface. © 2005 Elsevier B.V. All rights reserved.
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Comparative electrochemistry and electrocatalytic activities of cobalt, iron and manganese phthalocyanine complexes axially co-ordinated to mercaptopyridine self-assembled monolayer at gold electrodes
- Ozoemena, Kenneth I, Nyokong, Tebello
- Authors: Ozoemena, Kenneth I , Nyokong, Tebello
- Date: 2006
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/286054 , vital:56234 , xlink:href="https://doi.org/10.1016/j.electacta.2005.08.007"
- Description: Comparative surface electrochemistry and electrocatalytic properties of solid ultrathin monolayer films of metallophthalocyanine (MPc) complexes of cobalt (CoPc), iron (FePc) and manganese (MnPc) self-immobilised, via axial ligation reaction, onto preformed 4-mercaptopyridine self-assembled monolayers (SAMs) on gold electrodes have been described. Surface electrochemical parameters of the modified electrodes showed that these MPc-SAMs are densely packed with flat orientations. The electrochemical, electrocatalytic and stability properties of these MPc complexes follow this order: FePc > MnPc > CoPc. This finding is remarkable as it suggests that the success of using this method of self-assembling of MPc onto gold electrode is largely dependent on the bond distance between the pyridine linker and the central metal of the MPc; the shorter the distance, the faster the co-ordination and the better the electrocatalytic properties towards L-cysteine and thiocyanate. Thus, the superiority of FePc-based SAM over those of the MnPc and CoPc, has been proposed to be the result of the more favorable axial co-ordination properties of FePc with pyridine (i.e. shorter Fe–N(pyridine) bond length.
- Full Text:
- Authors: Ozoemena, Kenneth I , Nyokong, Tebello
- Date: 2006
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/286054 , vital:56234 , xlink:href="https://doi.org/10.1016/j.electacta.2005.08.007"
- Description: Comparative surface electrochemistry and electrocatalytic properties of solid ultrathin monolayer films of metallophthalocyanine (MPc) complexes of cobalt (CoPc), iron (FePc) and manganese (MnPc) self-immobilised, via axial ligation reaction, onto preformed 4-mercaptopyridine self-assembled monolayers (SAMs) on gold electrodes have been described. Surface electrochemical parameters of the modified electrodes showed that these MPc-SAMs are densely packed with flat orientations. The electrochemical, electrocatalytic and stability properties of these MPc complexes follow this order: FePc > MnPc > CoPc. This finding is remarkable as it suggests that the success of using this method of self-assembling of MPc onto gold electrode is largely dependent on the bond distance between the pyridine linker and the central metal of the MPc; the shorter the distance, the faster the co-ordination and the better the electrocatalytic properties towards L-cysteine and thiocyanate. Thus, the superiority of FePc-based SAM over those of the MnPc and CoPc, has been proposed to be the result of the more favorable axial co-ordination properties of FePc with pyridine (i.e. shorter Fe–N(pyridine) bond length.
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Synthesis and electrochemical characterisation of α-and β-tetra-substituted oxo (phthalocyaninato) titanium (IV) complexes
- Tau, Prudence, Nyokong, Tebello
- Authors: Tau, Prudence , Nyokong, Tebello
- Date: 2006
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/283869 , vital:55998 , xlink:href="https://doi.org/10.1016/j.poly.2005.11.025"
- Description: The synthesis, spectroscopic and electrochemical characterisation of the following oxotitanium tetra-substituted phthalocyanines are reported: 1,(4)-(tetraphenoxyphthalocyaninato)titanium(IV) oxide (5a); 1,(4)-(tetra-tert-butylphenoxyphthalocyaninato)titanium(IV) oxide (5b); 2,(3)-(tetraphenoxyphthalocyaninato)titanium(IV) oxide (6a) and 2,(3)-(tetra-tert-butylphenoxyphthalocyaninato)titanium(IV) oxide (6b). Complexes 5a and 5b are substituted at the non-peripheral (α) positions, whereas complexes 6a and 6b are substituted at the peripheral (β) positions. Cyclic voltammograms of all four complexes are similar, with three reversible reduction couples and three quasi-reversible to irreversible oxidations. The first two reductions are two-electron processes, confirmed by spectroelectrochemistry to be due to TiIVPc−2/TiIIPc−3 and TiIIPc−2/TiIPc−3 redox processes. Spectroelectrochemistry showed that upon oxidation, the molecule decomposes. Oxidation is expected to occur at the ring. Chronocoulometry confirmed two electron transfer at the first and second reduction steps; and a one electron transfer at the third reduction.
- Full Text:
- Authors: Tau, Prudence , Nyokong, Tebello
- Date: 2006
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/283869 , vital:55998 , xlink:href="https://doi.org/10.1016/j.poly.2005.11.025"
- Description: The synthesis, spectroscopic and electrochemical characterisation of the following oxotitanium tetra-substituted phthalocyanines are reported: 1,(4)-(tetraphenoxyphthalocyaninato)titanium(IV) oxide (5a); 1,(4)-(tetra-tert-butylphenoxyphthalocyaninato)titanium(IV) oxide (5b); 2,(3)-(tetraphenoxyphthalocyaninato)titanium(IV) oxide (6a) and 2,(3)-(tetra-tert-butylphenoxyphthalocyaninato)titanium(IV) oxide (6b). Complexes 5a and 5b are substituted at the non-peripheral (α) positions, whereas complexes 6a and 6b are substituted at the peripheral (β) positions. Cyclic voltammograms of all four complexes are similar, with three reversible reduction couples and three quasi-reversible to irreversible oxidations. The first two reductions are two-electron processes, confirmed by spectroelectrochemistry to be due to TiIVPc−2/TiIIPc−3 and TiIIPc−2/TiIPc−3 redox processes. Spectroelectrochemistry showed that upon oxidation, the molecule decomposes. Oxidation is expected to occur at the ring. Chronocoulometry confirmed two electron transfer at the first and second reduction steps; and a one electron transfer at the third reduction.
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