Comparative electrooxidation of nitrite by electrodeposited Co (II), Fe (II) and Mn (III) tetrakis (benzylmercapto) and tetrakis (dodecylmercapto) phthalocyanines on gold electrodes
- Agboola, Bolade, Nyokong, Tebello
- Authors: Agboola, Bolade , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/281212 , vital:55702 , xlink:href="https://doi.org/10.1016/j.aca.2007.01.031"
- Description: This work reports on the electrooxidation of nitrite using Co(II), Fe(II) and Mn(III) tetrakis (benzylmercapto) and tetrakis (dodecylmercapto) phthalocyanines electrodeposited onto a gold electrode. Good catalytic activity (in terms of lowering overpotential) was obtained for these molecules when compared to previously reported MPc catalysts. The catalytic current was found to vary linearly with nitrite concentration in the range employed in this work (0.1–1 mM) and high sensitivities ranging from 6.9 to 9.9 μA mM−1 were observed for all the modified electrodes.
- Full Text:
- Date Issued: 2007
- Authors: Agboola, Bolade , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/281212 , vital:55702 , xlink:href="https://doi.org/10.1016/j.aca.2007.01.031"
- Description: This work reports on the electrooxidation of nitrite using Co(II), Fe(II) and Mn(III) tetrakis (benzylmercapto) and tetrakis (dodecylmercapto) phthalocyanines electrodeposited onto a gold electrode. Good catalytic activity (in terms of lowering overpotential) was obtained for these molecules when compared to previously reported MPc catalysts. The catalytic current was found to vary linearly with nitrite concentration in the range employed in this work (0.1–1 mM) and high sensitivities ranging from 6.9 to 9.9 μA mM−1 were observed for all the modified electrodes.
- Full Text:
- Date Issued: 2007
Comparative electrooxidation of sulphite by self-assembled monolayers (SAMs) of Co (II), Fe (II), Ni (II) and Mn (III) tetrakis benzylmercapto and dodecylmercapto metallophthalocyanines complexes on gold electrodes
- Agboola, Bolade, Nyokong, Tebello
- Authors: Agboola, Bolade , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/281223 , vital:55703 , xlink:href="https://doi.org/10.1016/j.talanta.2006.11.042"
- Description: This work reports on the use of Co(II), Fe(II), Mn(III) and Ni(II) tetrakis benzylmercapto and dodecylmercapto phthalocyanine complexes for gold electrode modification for electrooxidation of sulphite ions. The complexes were successfully used to modify gold electrodes by self-assembled monolayer (SAM) technique. The self-assembled films are stable and showed blocking characteristics towards the following Faradaic processes; gold surface oxidation, underpotential deposition (UPD) of copper and solution redox chemistry of [Fe(H2O)63+]/[Fe(H2O)62+]. All the modified electrodes showed improved catalytic activities than the unmodified gold electrode towards sulphite ion electrooxidation with all the modified electrodes exhibiting high resistance to electrode surface passivation. Better catalytic performance were obtained for the CoPcs, FePcs and MnPcs which have metal based redox processes within the range of the sulphite electrooxidation peak, while the NiPcs which did not show metal based redox reaction performed less. The catalytic current was found to be linear with sulphite ion concentration in the concentration range employed in this work (0.1–1 mM) and sensitivities ranging from 1.68 to 2.96 μA/mM were observed for all the modified electrodes. Mechanisms of the catalytic oxidation of sulphite ions are proposed.
- Full Text:
- Date Issued: 2007
- Authors: Agboola, Bolade , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/281223 , vital:55703 , xlink:href="https://doi.org/10.1016/j.talanta.2006.11.042"
- Description: This work reports on the use of Co(II), Fe(II), Mn(III) and Ni(II) tetrakis benzylmercapto and dodecylmercapto phthalocyanine complexes for gold electrode modification for electrooxidation of sulphite ions. The complexes were successfully used to modify gold electrodes by self-assembled monolayer (SAM) technique. The self-assembled films are stable and showed blocking characteristics towards the following Faradaic processes; gold surface oxidation, underpotential deposition (UPD) of copper and solution redox chemistry of [Fe(H2O)63+]/[Fe(H2O)62+]. All the modified electrodes showed improved catalytic activities than the unmodified gold electrode towards sulphite ion electrooxidation with all the modified electrodes exhibiting high resistance to electrode surface passivation. Better catalytic performance were obtained for the CoPcs, FePcs and MnPcs which have metal based redox processes within the range of the sulphite electrooxidation peak, while the NiPcs which did not show metal based redox reaction performed less. The catalytic current was found to be linear with sulphite ion concentration in the concentration range employed in this work (0.1–1 mM) and sensitivities ranging from 1.68 to 2.96 μA/mM were observed for all the modified electrodes. Mechanisms of the catalytic oxidation of sulphite ions are proposed.
- Full Text:
- Date Issued: 2007
Electrocatalytic oxidation of chlorophenols by electropolymerised nickel (II) tetrakis benzylmercapto and dodecylmercapto metallophthalocyanines complexes on gold electrodes
- Agboola, Bolade, Nyokong, Tebello
- Authors: Agboola, Bolade , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/281247 , vital:55705 , xlink:href="https://doi.org/10.1016/j.electacta.2007.02.017"
- Description: This work reports on the use of nickel(II) tetrakis benzylmercapto (NiTBMPc) and dodecylmercapto (NiTDMPc) metallophthalocyanine complexes films on gold electrodes for the electrochemical oxidation of 4-chlorophenol (4-CP) and 2,4,5-trichlorophenol (TCP). Both NiTBMPc and NiTDMPc complexes were successfully deposited on gold electrodes by electropolymerisation. The films were electro-transformed in aqueous 0.1 M NaOH solution to the ‘O–Ni–O oxo’ bridged form. For both complexes, films with different thickness were prepared and characterised by electrochemical impedance and UV–vis (on indium tin oxide) spectroscopies and the results showed typical behaviour for modified electrodes with increasing charge transfer resistance values (Rp) with polymer thickness. The poly-Ni(OH)NiPcs showed better catalytic activity than their poly-NiPcs counterparts.
- Full Text:
- Date Issued: 2007
- Authors: Agboola, Bolade , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/281247 , vital:55705 , xlink:href="https://doi.org/10.1016/j.electacta.2007.02.017"
- Description: This work reports on the use of nickel(II) tetrakis benzylmercapto (NiTBMPc) and dodecylmercapto (NiTDMPc) metallophthalocyanine complexes films on gold electrodes for the electrochemical oxidation of 4-chlorophenol (4-CP) and 2,4,5-trichlorophenol (TCP). Both NiTBMPc and NiTDMPc complexes were successfully deposited on gold electrodes by electropolymerisation. The films were electro-transformed in aqueous 0.1 M NaOH solution to the ‘O–Ni–O oxo’ bridged form. For both complexes, films with different thickness were prepared and characterised by electrochemical impedance and UV–vis (on indium tin oxide) spectroscopies and the results showed typical behaviour for modified electrodes with increasing charge transfer resistance values (Rp) with polymer thickness. The poly-Ni(OH)NiPcs showed better catalytic activity than their poly-NiPcs counterparts.
- Full Text:
- Date Issued: 2007
Synthesis and electrochemical properties of benzyl-mercapto and dodecyl-mercapto tetrasubstituted manganese phthalocyanine complexes
- Agboola, Bolade, Ozoemena, Kenneth I, Westbroek, Philippe, Nyokong, Tebello
- Authors: Agboola, Bolade , Ozoemena, Kenneth I , Westbroek, Philippe , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/281321 , vital:55713 , xlink:href="https://doi.org/10.1016/j.electacta.2006.09.002"
- Description: Manganese tetrakis (benzyl-mercapto) phthalocyanine (MnTBMPc) and manganese tetrakis (dodecyl-mercapto) phthalocyanine (MnTDMPc) complexes were synthesized and their spectral and electrochemical properties are reported. Cyclic voltammetric data showed three reversible to quasi-reversible and two irreversible redox processes for both complexes. Ring substituents influenced the positions of both oxidation and reduction redox couples. Spectroelectrochemistry confirmed the first two reductions to be due to MnIIIPc2−/MnIIPc2− and MnIIPc3−/MnIIPc2− processes. The first example of a formation of self-assembled monolayers (SAMs) using thiol substituted MnPc complexes is presented, the SAMs were found to show blocking characteristics towards some faradaic reactions.
- Full Text:
- Date Issued: 2007
- Authors: Agboola, Bolade , Ozoemena, Kenneth I , Westbroek, Philippe , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/281321 , vital:55713 , xlink:href="https://doi.org/10.1016/j.electacta.2006.09.002"
- Description: Manganese tetrakis (benzyl-mercapto) phthalocyanine (MnTBMPc) and manganese tetrakis (dodecyl-mercapto) phthalocyanine (MnTDMPc) complexes were synthesized and their spectral and electrochemical properties are reported. Cyclic voltammetric data showed three reversible to quasi-reversible and two irreversible redox processes for both complexes. Ring substituents influenced the positions of both oxidation and reduction redox couples. Spectroelectrochemistry confirmed the first two reductions to be due to MnIIIPc2−/MnIIPc2− and MnIIPc3−/MnIIPc2− processes. The first example of a formation of self-assembled monolayers (SAMs) using thiol substituted MnPc complexes is presented, the SAMs were found to show blocking characteristics towards some faradaic reactions.
- Full Text:
- Date Issued: 2007
Voltammetric characterisation of the self-assembled monolayers (SAMs) of benzyl-and dodecyl-mercapto tetra substituted metallophthalocyanines complexes
- Agboola, Bolade, Westbroek, Philippe, Ozoemena, Kenneth I, Nyokong, Tebello
- Authors: Agboola, Bolade , Westbroek, Philippe , Ozoemena, Kenneth I , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/281414 , vital:55723 , xlink:href="https://doi.org/10.1016/j.elecom.2006.08.047"
- Description: Voltammetric characterisations of cobalt, iron, manganese, nickel and zinc phthalocyanine complexes tetra substituted with benzyl- and dodecyl-mercapto ring substituents and immobilisation on gold electrodes via the self-assembling technique are presented. The self-assembled films are stable and showed blocking characteristics towards the following Faradaic processes; gold surface oxidation, under potential deposition of copper and solution redox chemistry of [Fe(H2O)6 3+ ]/[Fe(H2O)6 2+ ]. The solution chemistry of [Fe(CN)6]−3/[Fe(CN)6]−4 redox process was used to study the orientation of the CoPcs-SAMs and this revealed a possible deviation from flat orientation of the complexes on the gold electrodes when the SAM formation times were greater than 24 h. For SAM formation time at 24 and 48 h, CoTDMPc-SAM showed more inhibition of the [Fe(CN)6]−3/[Fe(CN)6]−4 redox process than the CoTBMPc-SAM counterpart, indicating more blocking characteristics of the dodecylmercapto ring substituents compared to the benzylmercapto counterpart. To avoid SAM desorption, the potential application should be limited to −0.2 to +0.8 V vs. Ag∣AgCl (NaCl, sat’d) in acidic and neutral pH.
- Full Text:
- Date Issued: 2007
- Authors: Agboola, Bolade , Westbroek, Philippe , Ozoemena, Kenneth I , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/281414 , vital:55723 , xlink:href="https://doi.org/10.1016/j.elecom.2006.08.047"
- Description: Voltammetric characterisations of cobalt, iron, manganese, nickel and zinc phthalocyanine complexes tetra substituted with benzyl- and dodecyl-mercapto ring substituents and immobilisation on gold electrodes via the self-assembling technique are presented. The self-assembled films are stable and showed blocking characteristics towards the following Faradaic processes; gold surface oxidation, under potential deposition of copper and solution redox chemistry of [Fe(H2O)6 3+ ]/[Fe(H2O)6 2+ ]. The solution chemistry of [Fe(CN)6]−3/[Fe(CN)6]−4 redox process was used to study the orientation of the CoPcs-SAMs and this revealed a possible deviation from flat orientation of the complexes on the gold electrodes when the SAM formation times were greater than 24 h. For SAM formation time at 24 and 48 h, CoTDMPc-SAM showed more inhibition of the [Fe(CN)6]−3/[Fe(CN)6]−4 redox process than the CoTBMPc-SAM counterpart, indicating more blocking characteristics of the dodecylmercapto ring substituents compared to the benzylmercapto counterpart. To avoid SAM desorption, the potential application should be limited to −0.2 to +0.8 V vs. Ag∣AgCl (NaCl, sat’d) in acidic and neutral pH.
- Full Text:
- Date Issued: 2007
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:
- Date Issued: 2006
- 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:
- Date Issued: 2006
Hydrogen peroxide oxidation of 2-chlorophenol and 2, 4, 5-trichlorophenol catalyzed by monomeric and aggregated cobalt tetrasulfophthalocyanine
- Agboola, Bolade, Ozoemena, Kenneth I, Nyokong, Tebello
- Authors: Agboola, Bolade , Ozoemena, Kenneth I , Nyokong, Tebello
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/289249 , vital:56612 , xlink:href="https://doi.org/10.1016/j.molcata.2004.10.041"
- Description: Cobalt tetrasulfophthalocyanine (CoTSPc) was used to catalyze the oxidation of 2-chlorophenol (2-CP) and 2,4,5-trichlorophenol (TCP) using hydrogen peroxide (H2O2) as the oxidant. This CoTSPc catalyzed hydrogen peroxide oxidation of chlorophenols resulted in the formation of different types of oxidation products depending on the solvent conditions. In water/methanol conditions (where CoTSPc is mainly monomeric, and unionized forms of the phenols), phenol and hydroquinone were the main oxidation products, while in phosphate buffer solutions (pH 7 and 10 for TCP and 2-CP, respectively, where CoTSPc is mainly aggregated, and ionized forms of the phenols), benzoquinone was the main product. In contrast to CoTSPc, other MTSPc complexes studied (AlTSPc, CuTSPc and NiTSPc) exhibited no detectable catalytic effect on the oxidation of chlorophenols under the experimental conditions employed, thus proving the effect of the central metal ions on efficient catalysis of chlorophenol. Reaction pathways are proposed based on the relative time of oxidation products formation.
- Full Text:
- Date Issued: 2005
- Authors: Agboola, Bolade , Ozoemena, Kenneth I , Nyokong, Tebello
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/289249 , vital:56612 , xlink:href="https://doi.org/10.1016/j.molcata.2004.10.041"
- Description: Cobalt tetrasulfophthalocyanine (CoTSPc) was used to catalyze the oxidation of 2-chlorophenol (2-CP) and 2,4,5-trichlorophenol (TCP) using hydrogen peroxide (H2O2) as the oxidant. This CoTSPc catalyzed hydrogen peroxide oxidation of chlorophenols resulted in the formation of different types of oxidation products depending on the solvent conditions. In water/methanol conditions (where CoTSPc is mainly monomeric, and unionized forms of the phenols), phenol and hydroquinone were the main oxidation products, while in phosphate buffer solutions (pH 7 and 10 for TCP and 2-CP, respectively, where CoTSPc is mainly aggregated, and ionized forms of the phenols), benzoquinone was the main product. In contrast to CoTSPc, other MTSPc complexes studied (AlTSPc, CuTSPc and NiTSPc) exhibited no detectable catalytic effect on the oxidation of chlorophenols under the experimental conditions employed, thus proving the effect of the central metal ions on efficient catalysis of chlorophenol. Reaction pathways are proposed based on the relative time of oxidation products formation.
- Full Text:
- Date Issued: 2005
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