4-Azidoaniline-based electropolymer as a building block for functionalisation of conductive surfaces
- Coates, Megan, Elamari, Hichem, Girard, Christian, Griveau, Sophie, Nyokong, Tebello, Bedioui, Fethi
- Authors: Coates, Megan , Elamari, Hichem , Girard, Christian , Griveau, Sophie , Nyokong, Tebello , Bedioui, Fethi
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/244404 , vital:51254 , xlink:href="https://doi.org/10.1016/j.jelechem.2012.01.001"
- Description: We propose in this work to compare three approaches using 4-azidoaniline combined with “click” chemistry and electrochemistry to anchor ferrocene moieties at glassy carbon surfaces. The immobilisation of a newly synthesised molecule, 4-(4-ferrocenyl-1H-1,2,3-triazol-1-yl)aniline, through direct electropolymerisation or via in situ diazotization followed by electrografting is studied by analysing the samples by XPS and electrochemistry.
- Full Text:
- Date Issued: 2012
4-Azidoaniline-based electropolymer as a building block for functionalisation of conductive surfaces
- Authors: Coates, Megan , Elamari, Hichem , Girard, Christian , Griveau, Sophie , Nyokong, Tebello , Bedioui, Fethi
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/244404 , vital:51254 , xlink:href="https://doi.org/10.1016/j.jelechem.2012.01.001"
- Description: We propose in this work to compare three approaches using 4-azidoaniline combined with “click” chemistry and electrochemistry to anchor ferrocene moieties at glassy carbon surfaces. The immobilisation of a newly synthesised molecule, 4-(4-ferrocenyl-1H-1,2,3-triazol-1-yl)aniline, through direct electropolymerisation or via in situ diazotization followed by electrografting is studied by analysing the samples by XPS and electrochemistry.
- Full Text:
- Date Issued: 2012
Cyclic voltammetry and spectroelectrochemistry of a novel manganese phthalocyanine substituted with hexynyl groups
- Quinton, Damien, Antunes, Edith M, Griveau, Sophie, Nyokong, Tebello, Bedioui, Fethi
- Authors: Quinton, Damien , Antunes, Edith M , Griveau, Sophie , Nyokong, Tebello , Bedioui, Fethi
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/248450 , vital:51687 , xlink:href="https://doi.org/10.1016/j.inoche.2010.11.029"
- Description: We report here on the synthesis of a new manganese phthalocyanine complex, namely Mn tetrakis(5-hexyn-oxy) phthalocyanine (3), specifically designed to possess an alkyne moiety for its potential use in controlled immobilization on electrodes via the so called “click” chemistry reaction. The electrochemical activity of complex 3 was investigated by cyclic voltammetry and the nature of the observed redox couples was elucidated by spectroelectrochemistry. This work has also shown that the reduction of Mn(III)Pc complex to Mn(II)Pc is accompanied by the formation of MnPc μ-oxo species. Further reduction results in the formation of Mn(II)Pc(− 3) rather than Mn(I)Pc(− 2).
- Full Text:
- Date Issued: 2011
- Authors: Quinton, Damien , Antunes, Edith M , Griveau, Sophie , Nyokong, Tebello , Bedioui, Fethi
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/248450 , vital:51687 , xlink:href="https://doi.org/10.1016/j.inoche.2010.11.029"
- Description: We report here on the synthesis of a new manganese phthalocyanine complex, namely Mn tetrakis(5-hexyn-oxy) phthalocyanine (3), specifically designed to possess an alkyne moiety for its potential use in controlled immobilization on electrodes via the so called “click” chemistry reaction. The electrochemical activity of complex 3 was investigated by cyclic voltammetry and the nature of the observed redox couples was elucidated by spectroelectrochemistry. This work has also shown that the reduction of Mn(III)Pc complex to Mn(II)Pc is accompanied by the formation of MnPc μ-oxo species. Further reduction results in the formation of Mn(II)Pc(− 3) rather than Mn(I)Pc(− 2).
- Full Text:
- Date Issued: 2011
Electro-catalyzed oxidation of reduced glutathione and 2-mercaptoethanol by cobalt phthalocyanine-containing screen printed graphite electrodes
- Sehlotho, Nthapo, Griveau, Sophie, Ruillé, Nadine, Boujtita, Mohammed, Nyokong, Tebello, Bedioui, Fethi
- Authors: Sehlotho, Nthapo , Griveau, Sophie , Ruillé, Nadine , Boujtita, Mohammed , Nyokong, Tebello , Bedioui, Fethi
- Date: 2008
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/265935 , vital:53902 , xlink:href="https://doi.org/10.1016/j.msec.2007.10.054"
- Description: Electro-catalytic behavior of screen printed graphite electrodes modified with cobalt phthalocyanine (CoPc) towards the oxidation of reduced glutathione (GSH) and 2-mercaptoethanol (2-ME) is reported. We find, by using cyclic voltammetry, that the oxidation of 2-ME occurs at 0.2 V vs Ag/AgCl and − 0.3 vs Ag/AgCl V at pH = 7 and pH = 13, respectively and that of GSH occurs at 0.4 V vs Ag/AgCl and 0.0 V vs Ag/AgCl at pH = 7 and 13, respectively. The electro-catalytic activity depends on the method of electrode modification and the amount of catalyst incorporated in the ink used to fabricate the SPCEs. The highest activity was obtained with electrodes prepared with 2.5% (w:w) of CoPc.
- Full Text:
- Date Issued: 2008
- Authors: Sehlotho, Nthapo , Griveau, Sophie , Ruillé, Nadine , Boujtita, Mohammed , Nyokong, Tebello , Bedioui, Fethi
- Date: 2008
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/265935 , vital:53902 , xlink:href="https://doi.org/10.1016/j.msec.2007.10.054"
- Description: Electro-catalytic behavior of screen printed graphite electrodes modified with cobalt phthalocyanine (CoPc) towards the oxidation of reduced glutathione (GSH) and 2-mercaptoethanol (2-ME) is reported. We find, by using cyclic voltammetry, that the oxidation of 2-ME occurs at 0.2 V vs Ag/AgCl and − 0.3 vs Ag/AgCl V at pH = 7 and pH = 13, respectively and that of GSH occurs at 0.4 V vs Ag/AgCl and 0.0 V vs Ag/AgCl at pH = 7 and 13, respectively. The electro-catalytic activity depends on the method of electrode modification and the amount of catalyst incorporated in the ink used to fabricate the SPCEs. The highest activity was obtained with electrodes prepared with 2.5% (w:w) of CoPc.
- Full Text:
- Date Issued: 2008
Electro-oxidation of phenol and its derivatives on poly-Ni (OH) TPhPyPc modified vitreous carbon electrodes
- Obirai, Joseph, Bedioui, Fethi, Nyokong, Tebello
- Authors: Obirai, Joseph , Bedioui, Fethi , Nyokong, Tebello
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/289353 , vital:56625 , xlink:href="https://doi.org/10.1016/j.jelechem.2004.11.006"
- Description: The electrochemical oxidation of phenol and its derivatives using poly-nickel hydroxy tetraphenoxypyrrolephthalocyanine (poly-Ni(OH)TPhPyPc) modified vitreous carbon electrodes are described. The films were formed by the electro-transformation of the electropolymerized pyrrole-substituted phenoxyphthalocyanine poly-NiTPhPyPc modified electrode in aqueous 0.1 M NaOH solution. The poly-Ni(OH)TPhPyPc films showed better stability and resistance to electrode fouling compared to poly-NiTPhPyPc and unmodified electrodes. The resistance to surface fouling and stability can be attributed to the structure of the ring substituent on the phthalocyanine macrocycle and to the particular O–Ni–O bridged architecture of the nickel phthalocyanine film.
- Full Text:
- Date Issued: 2005
- Authors: Obirai, Joseph , Bedioui, Fethi , Nyokong, Tebello
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/289353 , vital:56625 , xlink:href="https://doi.org/10.1016/j.jelechem.2004.11.006"
- Description: The electrochemical oxidation of phenol and its derivatives using poly-nickel hydroxy tetraphenoxypyrrolephthalocyanine (poly-Ni(OH)TPhPyPc) modified vitreous carbon electrodes are described. The films were formed by the electro-transformation of the electropolymerized pyrrole-substituted phenoxyphthalocyanine poly-NiTPhPyPc modified electrode in aqueous 0.1 M NaOH solution. The poly-Ni(OH)TPhPyPc films showed better stability and resistance to electrode fouling compared to poly-NiTPhPyPc and unmodified electrodes. The resistance to surface fouling and stability can be attributed to the structure of the ring substituent on the phthalocyanine macrocycle and to the particular O–Ni–O bridged architecture of the nickel phthalocyanine film.
- Full Text:
- Date Issued: 2005
Metallophthalocyanine-based molecular materials as catalysts for electrochemical reactions
- Zagal, José H, Griveau, Sophie J, Silva, Francisco, Nyokong, Tebello, Bedioui, Fethi
- Authors: Zagal, José H , Griveau, Sophie J , Silva, Francisco , Nyokong, Tebello , Bedioui, Fethi
- Date: 2010
- Language: English
- Type: text , Article
- Identifier: vital:7239 , http://hdl.handle.net/10962/d1019718
- Description: Metallophthalocyanines confined on the surface of electrodes are active catalysts for a large variety of electrochemical reactions and electrode surfaces modified by these complexes can be obtained by simple adsorption on graphite and carbon. However, more stable electrodes can be achieved by coating their surfaces with electropolymerized layers of the complexes, that show similar activity than their monomer counterparts. In all cases, fundamental studies carried out with adsorbed layers of these complexes have shown that the redox potential is a very good reactivity index for predicting the catalytic activity of the complexes. Volcano-shaped correlations have been found between the electrocatalytic activity (as log I at constant E) versus the Co(II)/(I) formal potential (E°′) of Co-macrocyclics for the oxidation of several thiols, hydrazine and glucose. For the electroreduction of O2 only linear correlations between the electrocatalytic activity versus the M(III)/M(II) formal potential have been found using Cr, Mn, Fe and Co phthalocyanines but it is likely that these correlations are “incomplete volcano” correlations. The volcano correlations strongly suggest that E°′, the formal potential of the complex needs to be in a rather narrow potential window for achieving maximum activity, probably corresponding to surface coverages of an M-molecule adduct equal to 0.5 and to standard free energies of adsorption of the reacting molecule on the complex active site equal to zero. These results indicate that the catalytic activity of metallophthalocyanines for the oxidation of several molecules can be “tuned” by manipulating the E°′ formal potential, using proper groups on the macrocyclic ligand. This review emphasizes once more that metallophthalocyanines are extremely versatile materials with many applications in electrocatalysis, electroanalysis, just to mention a few, and they provide very good models for testing their catalytic activity for several reactions. Even though the earlier applications of these complexes were focused on providing active materials for electroreduction of O2, for making active cathodes for fuel cells, the main trend in the literature nowadays is to use these complexes for making active electrodes for electrochemical sensors. , Original publication is available at http://dx.doi.org/10.1016/j.ccr.2010.05.001
- Full Text: false
- Date Issued: 2010
- Authors: Zagal, José H , Griveau, Sophie J , Silva, Francisco , Nyokong, Tebello , Bedioui, Fethi
- Date: 2010
- Language: English
- Type: text , Article
- Identifier: vital:7239 , http://hdl.handle.net/10962/d1019718
- Description: Metallophthalocyanines confined on the surface of electrodes are active catalysts for a large variety of electrochemical reactions and electrode surfaces modified by these complexes can be obtained by simple adsorption on graphite and carbon. However, more stable electrodes can be achieved by coating their surfaces with electropolymerized layers of the complexes, that show similar activity than their monomer counterparts. In all cases, fundamental studies carried out with adsorbed layers of these complexes have shown that the redox potential is a very good reactivity index for predicting the catalytic activity of the complexes. Volcano-shaped correlations have been found between the electrocatalytic activity (as log I at constant E) versus the Co(II)/(I) formal potential (E°′) of Co-macrocyclics for the oxidation of several thiols, hydrazine and glucose. For the electroreduction of O2 only linear correlations between the electrocatalytic activity versus the M(III)/M(II) formal potential have been found using Cr, Mn, Fe and Co phthalocyanines but it is likely that these correlations are “incomplete volcano” correlations. The volcano correlations strongly suggest that E°′, the formal potential of the complex needs to be in a rather narrow potential window for achieving maximum activity, probably corresponding to surface coverages of an M-molecule adduct equal to 0.5 and to standard free energies of adsorption of the reacting molecule on the complex active site equal to zero. These results indicate that the catalytic activity of metallophthalocyanines for the oxidation of several molecules can be “tuned” by manipulating the E°′ formal potential, using proper groups on the macrocyclic ligand. This review emphasizes once more that metallophthalocyanines are extremely versatile materials with many applications in electrocatalysis, electroanalysis, just to mention a few, and they provide very good models for testing their catalytic activity for several reactions. Even though the earlier applications of these complexes were focused on providing active materials for electroreduction of O2, for making active cathodes for fuel cells, the main trend in the literature nowadays is to use these complexes for making active electrodes for electrochemical sensors. , Original publication is available at http://dx.doi.org/10.1016/j.ccr.2010.05.001
- Full Text: false
- Date Issued: 2010
Microelectrochemical patterning of gold surfaces using 4-azidobenzenediazonium and scanning electrochemical microscopy
- Coates, Megan, Cabet, Eva, Griveau, Sophie, Nyokong, Tebello, Bedioui, Fethi
- Authors: Coates, Megan , Cabet, Eva , Griveau, Sophie , Nyokong, Tebello , Bedioui, Fethi
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/247926 , vital:51630 , xlink:href="https://doi.org/10.1016/j.elecom.2010.11.037"
- Description: This work describes for the first time the possibility of performing local micro electrochemical grafting of a gold substrate by 4-azidobenzenediazonium by SECM in a single and simple one step without complications from adsorption. The electrografted spots of diazonium were performed by positioning a Pt tip at a given distance above the gold substrate and the SECM was used in a three-electrode configuration (the Pt tip serving as the microanode) in acetonitrile containing 5 mM 4-azidobenzenediazonium and 0.1 M Bu4NBF4 during 10 ms. The dimensions of the derivatized areas of the substrates were finely tuned by using different experimental conditions (tip distance above the substrate, tip diameter, presence or absence of supporting electrolyte). The use of the azido-derivated diazonium molecule and these preliminary results open the gate to important applications and developments devoted to the local micro functionalization of electrodes by thin layers that allow the implementation of the emerging and attractive interfacial click reaction.
- Full Text:
- Date Issued: 2011
- Authors: Coates, Megan , Cabet, Eva , Griveau, Sophie , Nyokong, Tebello , Bedioui, Fethi
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/247926 , vital:51630 , xlink:href="https://doi.org/10.1016/j.elecom.2010.11.037"
- Description: This work describes for the first time the possibility of performing local micro electrochemical grafting of a gold substrate by 4-azidobenzenediazonium by SECM in a single and simple one step without complications from adsorption. The electrografted spots of diazonium were performed by positioning a Pt tip at a given distance above the gold substrate and the SECM was used in a three-electrode configuration (the Pt tip serving as the microanode) in acetonitrile containing 5 mM 4-azidobenzenediazonium and 0.1 M Bu4NBF4 during 10 ms. The dimensions of the derivatized areas of the substrates were finely tuned by using different experimental conditions (tip distance above the substrate, tip diameter, presence or absence of supporting electrolyte). The use of the azido-derivated diazonium molecule and these preliminary results open the gate to important applications and developments devoted to the local micro functionalization of electrodes by thin layers that allow the implementation of the emerging and attractive interfacial click reaction.
- Full Text:
- Date Issued: 2011
Surface patterning using scanning electrochemical microscopy to locally trigger a “click” chemistry reaction
- Quinton, Damien, Maringa, Audacity, Griveau, Sophie, Nyokong, Tebello, Bedioui, Fethi
- Authors: Quinton, Damien , Maringa, Audacity , Griveau, Sophie , Nyokong, Tebello , Bedioui, Fethi
- Language: English
- Type: Article
- Identifier: vital:7331 , http://hdl.handle.net/10962/d1020592
- Description: We report on the surface micropatterning of conductive surfaces via the electrochemical triggering of a click reaction, the copper(I) catalyzed azide–alkyne cycloaddition reaction (CuAAC) by SECM via a two-step approach: (i) functionalization on the entire surface with azido-aryl groups by using the diazonium approach followed by (ii) the covalent linkage of alkyne-bearing ferrocene by CuAAC within a local area by SECM. More precisely, the click reaction was triggered by Cu(I) catalyst generation for 30 min at the SECM tip positioned ≈ 10 μm above the azido-aryl modified surface. The dimension of the spot obtained under these conditions was ≈ 75 μm. The electrochemical imaging by SECM of the ultra thin area locally clicked with ferrocene moieties was made thanks to the electrocatalytic properties of the ferrocene modified surface towards ferrocyanide electrooxidation. This local clicking procedure opens the gate to further controlled functionalization of restricted small substrates. , Original publication is available at http://dx.doi.org/10.1016/j.elecom.2013.03.021
- Full Text: false
- Authors: Quinton, Damien , Maringa, Audacity , Griveau, Sophie , Nyokong, Tebello , Bedioui, Fethi
- Language: English
- Type: Article
- Identifier: vital:7331 , http://hdl.handle.net/10962/d1020592
- Description: We report on the surface micropatterning of conductive surfaces via the electrochemical triggering of a click reaction, the copper(I) catalyzed azide–alkyne cycloaddition reaction (CuAAC) by SECM via a two-step approach: (i) functionalization on the entire surface with azido-aryl groups by using the diazonium approach followed by (ii) the covalent linkage of alkyne-bearing ferrocene by CuAAC within a local area by SECM. More precisely, the click reaction was triggered by Cu(I) catalyst generation for 30 min at the SECM tip positioned ≈ 10 μm above the azido-aryl modified surface. The dimension of the spot obtained under these conditions was ≈ 75 μm. The electrochemical imaging by SECM of the ultra thin area locally clicked with ferrocene moieties was made thanks to the electrocatalytic properties of the ferrocene modified surface towards ferrocyanide electrooxidation. This local clicking procedure opens the gate to further controlled functionalization of restricted small substrates. , Original publication is available at http://dx.doi.org/10.1016/j.elecom.2013.03.021
- Full Text: false
Surface patterning using scanning electrochemical microscopy to locally trigger a “click” chemistry reaction
- Quinton, Damien, Maringa, Audacity, Griveau, Sophie, Nyokong, Tebello, Bedioui, Fethi
- Authors: Quinton, Damien , Maringa, Audacity , Griveau, Sophie , Nyokong, Tebello , Bedioui, Fethi
- Date: 2013
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241805 , vital:50971 , xlink:href="https://doi.org/10.1016/j.elecom.2013.03.021"
- Description: We report on the surface micropatterning of conductive surfaces via the electrochemical triggering of a click reaction, the copper(I) catalyzed azide–alkyne cycloaddition reaction (CuAAC) by SECM via a two-step approach: (i) functionalization on the entire surface with azido-aryl groups by using the diazonium approach followed by (ii) the covalent linkage of alkyne-bearing ferrocene by CuAAC within a local area by SECM. More precisely, the click reaction was triggered by Cu(I) catalyst generation for 30 min at the SECM tip positioned ≈ 10 μm above the azido-aryl modified surface. The dimension of the spot obtained under these conditions was ≈ 75 μm. The electrochemical imaging by SECM of the ultra thin area locally clicked with ferrocene moieties was made thanks to the electrocatalytic properties of the ferrocene modified surface towards ferrocyanide electrooxidation. This local clicking procedure opens the gate to further controlled functionalization of restricted small substrates.
- Full Text:
- Date Issued: 2013
- Authors: Quinton, Damien , Maringa, Audacity , Griveau, Sophie , Nyokong, Tebello , Bedioui, Fethi
- Date: 2013
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241805 , vital:50971 , xlink:href="https://doi.org/10.1016/j.elecom.2013.03.021"
- Description: We report on the surface micropatterning of conductive surfaces via the electrochemical triggering of a click reaction, the copper(I) catalyzed azide–alkyne cycloaddition reaction (CuAAC) by SECM via a two-step approach: (i) functionalization on the entire surface with azido-aryl groups by using the diazonium approach followed by (ii) the covalent linkage of alkyne-bearing ferrocene by CuAAC within a local area by SECM. More precisely, the click reaction was triggered by Cu(I) catalyst generation for 30 min at the SECM tip positioned ≈ 10 μm above the azido-aryl modified surface. The dimension of the spot obtained under these conditions was ≈ 75 μm. The electrochemical imaging by SECM of the ultra thin area locally clicked with ferrocene moieties was made thanks to the electrocatalytic properties of the ferrocene modified surface towards ferrocyanide electrooxidation. This local clicking procedure opens the gate to further controlled functionalization of restricted small substrates.
- Full Text:
- Date Issued: 2013
Tuning the redox properties of Co-N4 macrocyclic complexes for the catalytic electrooxidation of glucose
- Villagra, Evelyn, Bedioui, Fethi, Nyokong, Tebello, Canales, J Carlos, Sancy, Mamie, Páez, Maritza A, Costamagna, Juan, Zagal, Jose H
- Authors: Villagra, Evelyn , Bedioui, Fethi , Nyokong, Tebello , Canales, J Carlos , Sancy, Mamie , Páez, Maritza A , Costamagna, Juan , Zagal, Jose H
- Date: 2008
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/268675 , vital:54221 , xlink:href="https://doi.org/10.1016/j.electacta.2008.02.006"
- Description: Graphite electrodes modified with four different cobalt N4 macrocyclics, namely Co tetrapentapyridinophthalocyanine, (CoTPenPyrPc), Co tetrapyridinoporphyrazine (CoTPyPz), Co octa(hydroxyethylthio)phthalocyanine (CoOEHTPc) and Co tetranitrophthalocyanine (CoTNPc) exhibit catalytic activity for the oxidation of glucose in alkaline media. The purpose of this work is to establish correlations between the catalytic activity of these complexes and their redox potential. The activity of the different modified electrodes was tested by linear voltammetry under hydrodynamic conditions using the rotating disk technique. Tafel plots constructed from mass-transport corrected currents give slopes ranging from 0.080 to 0.160 V/decade for the different catalysts which suggests that a first one-electron step is rate controlling with the symmetry of the energy barrier depending on the nature of the ligand of the Co complex. A plot of log I versus the Co(II)/(I) formal potential gives a volcano curve that also includes catalysts studied previously. This illustrates the concept that the formal potential of the catalyst needs to be tuned to a certain value for achieving maximum activity. A theoretical interpretation of these results is given in terms of Langmuir isotherms for the adsorption of glucose on the Co sites of the surface-confined metal complexes.
- Full Text:
- Date Issued: 2008
- Authors: Villagra, Evelyn , Bedioui, Fethi , Nyokong, Tebello , Canales, J Carlos , Sancy, Mamie , Páez, Maritza A , Costamagna, Juan , Zagal, Jose H
- Date: 2008
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/268675 , vital:54221 , xlink:href="https://doi.org/10.1016/j.electacta.2008.02.006"
- Description: Graphite electrodes modified with four different cobalt N4 macrocyclics, namely Co tetrapentapyridinophthalocyanine, (CoTPenPyrPc), Co tetrapyridinoporphyrazine (CoTPyPz), Co octa(hydroxyethylthio)phthalocyanine (CoOEHTPc) and Co tetranitrophthalocyanine (CoTNPc) exhibit catalytic activity for the oxidation of glucose in alkaline media. The purpose of this work is to establish correlations between the catalytic activity of these complexes and their redox potential. The activity of the different modified electrodes was tested by linear voltammetry under hydrodynamic conditions using the rotating disk technique. Tafel plots constructed from mass-transport corrected currents give slopes ranging from 0.080 to 0.160 V/decade for the different catalysts which suggests that a first one-electron step is rate controlling with the symmetry of the energy barrier depending on the nature of the ligand of the Co complex. A plot of log I versus the Co(II)/(I) formal potential gives a volcano curve that also includes catalysts studied previously. This illustrates the concept that the formal potential of the catalyst needs to be tuned to a certain value for achieving maximum activity. A theoretical interpretation of these results is given in terms of Langmuir isotherms for the adsorption of glucose on the Co sites of the surface-confined metal complexes.
- Full Text:
- Date Issued: 2008
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