Carbon nanotube-enhanced photoelectrochemical properties of metallo-octacarboxyphthalocyanines
- Mphahlele, Nonhlanhla E, Le Roux, Lukas, Jafta, Charl J, Cele, Leskev, Mathe, Mkhulu K, Nyokong, Tebello, Kobayashi, Nagao, Ozoemena, Kenneth I
- Authors: Mphahlele, Nonhlanhla E , Le Roux, Lukas , Jafta, Charl J , Cele, Leskev , Mathe, Mkhulu K , Nyokong, Tebello , Kobayashi, Nagao , Ozoemena, Kenneth I
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241595 , vital:50953 , xlink:href="https://doi.org/10.1007/s10853-013-7710-1"
- Description: The photoelectrochemistry of metallo-octacarboxyphthalocyanines (MOCPc, where M = Zn or Si(OH)2) integrated with MWCNTs for the development of dye-sensitized solar cells (DSSCs) is reported. The DSSC performance (obtained from the photo-chronoamperometric and photo-impedimetric data) decreased as ZnOCPc > (OH)2SiOCPc. The incorporation of the MWCNTs on the surface of the TiO2 film (MOCPc–MWCNT systems) gave higher photocurrent density than the bare MOCPc complexes. Also, from the EIS results, the MOCPc–MWCNT hybrids gave faster charge transport kinetics (approximately three times faster) compared to the bare MOCPc complexes. The electron lifetime was slightly longer (ca. 6 ms) at the ZnOCPc systems than at the (OH)2SiOCPc system (ca. 4 ms) meaning that the presence of the MWCNTs on the surface of the TiO2 film did not show any significant improvement on preventing charge recombination process.
- Full Text:
- Date Issued: 2014
- Authors: Mphahlele, Nonhlanhla E , Le Roux, Lukas , Jafta, Charl J , Cele, Leskev , Mathe, Mkhulu K , Nyokong, Tebello , Kobayashi, Nagao , Ozoemena, Kenneth I
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241595 , vital:50953 , xlink:href="https://doi.org/10.1007/s10853-013-7710-1"
- Description: The photoelectrochemistry of metallo-octacarboxyphthalocyanines (MOCPc, where M = Zn or Si(OH)2) integrated with MWCNTs for the development of dye-sensitized solar cells (DSSCs) is reported. The DSSC performance (obtained from the photo-chronoamperometric and photo-impedimetric data) decreased as ZnOCPc > (OH)2SiOCPc. The incorporation of the MWCNTs on the surface of the TiO2 film (MOCPc–MWCNT systems) gave higher photocurrent density than the bare MOCPc complexes. Also, from the EIS results, the MOCPc–MWCNT hybrids gave faster charge transport kinetics (approximately three times faster) compared to the bare MOCPc complexes. The electron lifetime was slightly longer (ca. 6 ms) at the ZnOCPc systems than at the (OH)2SiOCPc system (ca. 4 ms) meaning that the presence of the MWCNTs on the surface of the TiO2 film did not show any significant improvement on preventing charge recombination process.
- Full Text:
- Date Issued: 2014
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
Electrocatalytic oxidation and detection of hydrazine at gold electrode modified with iron phthalocyanine complex linked to mercaptopyridine self-assembled monolayer
- Ozoemena, Kenneth I, Nyokong, Tebello
- Authors: Ozoemena, Kenneth I , Nyokong, Tebello
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/286065 , vital:56235 , xlink:href="https://doi.org/10.1016/j.talanta.2005.02.030"
- Description: Electrocatalytic oxidation and detection of hydrazine in pH 7.0 conditions were studied by using gold electrode modified with self-assembled monolayer (SAM) films of iron phthalocyanine (FePc) complex axially ligated to a preformed 4-mercaptopyridine SAMs. The anodic oxidation of hydrazine in neutral pH conditions with FePc-linked-mercaptopyridine-SAM-modified gold electrode occurred at low overpotential (0.35 V versus Ag|AgCl) and the treatment of the voltammetric data showed that it was a pure diffusion-controlled reaction with the involvement of one electron in the rate-determining step. The mechanism for the interaction of hydrazine with the FePc-SAM is proposed to involve the Fe(III)Pc/Fe(II)Pc redox process. Using cyclic voltammetry (CV) and Osteryoung square wave voltammetry (OSWV), hydrazine was detected over a linear concentration range of 1.3 × 10−5 to 9.2 × 10−5 mol/L with low limits of detection (ca. 5 and 11 μM for OSWV and CV, respectively). At concentrations higher than 1.2 × 10−4 mol/L the anodic peak potential shifted to 0.40 V (versus Ag|AgCl), and this was interpreted to be due to kinetic limitations resulting from the saturation of hydrazine and its oxidation products onto the redox-active monolayer film. This type of metallophthalocyanine-SAM-based electrode is a highly promising electrochemical sensor given its ease of fabrication, good catalytic activity, stability, sensitivity and simplicity.
- Full Text:
- Date Issued: 2005
- Authors: Ozoemena, Kenneth I , Nyokong, Tebello
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/286065 , vital:56235 , xlink:href="https://doi.org/10.1016/j.talanta.2005.02.030"
- Description: Electrocatalytic oxidation and detection of hydrazine in pH 7.0 conditions were studied by using gold electrode modified with self-assembled monolayer (SAM) films of iron phthalocyanine (FePc) complex axially ligated to a preformed 4-mercaptopyridine SAMs. The anodic oxidation of hydrazine in neutral pH conditions with FePc-linked-mercaptopyridine-SAM-modified gold electrode occurred at low overpotential (0.35 V versus Ag|AgCl) and the treatment of the voltammetric data showed that it was a pure diffusion-controlled reaction with the involvement of one electron in the rate-determining step. The mechanism for the interaction of hydrazine with the FePc-SAM is proposed to involve the Fe(III)Pc/Fe(II)Pc redox process. Using cyclic voltammetry (CV) and Osteryoung square wave voltammetry (OSWV), hydrazine was detected over a linear concentration range of 1.3 × 10−5 to 9.2 × 10−5 mol/L with low limits of detection (ca. 5 and 11 μM for OSWV and CV, respectively). At concentrations higher than 1.2 × 10−4 mol/L the anodic peak potential shifted to 0.40 V (versus Ag|AgCl), and this was interpreted to be due to kinetic limitations resulting from the saturation of hydrazine and its oxidation products onto the redox-active monolayer film. This type of metallophthalocyanine-SAM-based electrode is a highly promising electrochemical sensor given its ease of fabrication, good catalytic activity, stability, sensitivity and simplicity.
- Full Text:
- Date Issued: 2005
Surface electrochemistry of iron phthalocyanine axially ligated to 4-mercaptopyridine self-assembled monolayers at gold electrode
- Ozoemena, Kenneth I, Nyokong, Tebello
- Authors: Ozoemena, Kenneth I , Nyokong, Tebello
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/289282 , vital:56615 , xlink:href="https://doi.org/10.1016/j.jelechem.2005.02.018"
- Description: Surface electrochemical behaviour of a self-immobilised iron phthalocyanine (FePc) ultrathin film, via axial ligation reaction, onto a preformed 4-mercaptopyridine self-assembled monolayer on gold electrode has been described. Electrochemical evidence for the sensor clearly suggested surface-confined, flat “umbrella”-oriented and densely-packed monolayer film structure. The proposed electrochemical sensor exhibited good catalytic activity towards the oxidation of thiocyanate in pH 4.0 medium over a linear range of three decades of concentration (ca. 10−6–10−3 mol dm−3) with a detection limit in the order of ∼10−7 mol dm−3. The sensor exhibited useful potential for the analysis of thiocyanate in human urine and saliva samples. The advantageous properties of this type of electrode as a sensor for thiocyanate lie in its ease of fabrication, excellent catalytic activity, stability, sensitivity and simplicity.
- Full Text:
- Date Issued: 2005
- Authors: Ozoemena, Kenneth I , Nyokong, Tebello
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/289282 , vital:56615 , xlink:href="https://doi.org/10.1016/j.jelechem.2005.02.018"
- Description: Surface electrochemical behaviour of a self-immobilised iron phthalocyanine (FePc) ultrathin film, via axial ligation reaction, onto a preformed 4-mercaptopyridine self-assembled monolayer on gold electrode has been described. Electrochemical evidence for the sensor clearly suggested surface-confined, flat “umbrella”-oriented and densely-packed monolayer film structure. The proposed electrochemical sensor exhibited good catalytic activity towards the oxidation of thiocyanate in pH 4.0 medium over a linear range of three decades of concentration (ca. 10−6–10−3 mol dm−3) with a detection limit in the order of ∼10−7 mol dm−3. The sensor exhibited useful potential for the analysis of thiocyanate in human urine and saliva samples. The advantageous properties of this type of electrode as a sensor for thiocyanate lie in its ease of fabrication, excellent catalytic activity, stability, sensitivity and simplicity.
- Full Text:
- Date Issued: 2005
Electrochemical behaviour of thiol-derivatised zinc (II) phthalocyanine complexes and their self-immobilised films at gold electrodes
- Ozoemena, Kenneth I, Nyokong, Tebello
- Authors: Ozoemena, Kenneth I , Nyokong, Tebello
- Date: 2003
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/290295 , vital:56737 , xlink:href="https://doi.org/10.1016/j.microc.2003.08.002"
- Description: Electrochemical properties of novel, peripherally substituted zinc phthalocyanine complex, octa(4-methylphenylthio-) phthalocyaninatozinc(II) [ZnPc(SC6H4CH3)8] (1a) in DMF solution are presented. This complex showed five quasi-reversible/reversible, diffusion-controlled redox couples. Solution voltammetry of 1a showed little contrast with that of its alkythiol-derivative, octabutylthiophthalocyaninatozinc(II) [ZnPc(SC4H9)8] (1b) in that both thiol-substituents tend to show electron-withdrawing influence on the phthalocyanine ligands; complex 1a showing easier reduction and more difficult to oxidation when compared to 1b and other alkyl derivatives. The voltammetric features of the solid ultrathin films of 1a and 1b, immobilized on gold electrodes via the self-assembling technique, are also presented. Interestingly, the self-assembled films are stable and reproducible and provide good suppression to the following Faradaic processes; gold surface oxidation, solution ion species and underpotential deposition (UPD) of copper.
- Full Text:
- Date Issued: 2003
- Authors: Ozoemena, Kenneth I , Nyokong, Tebello
- Date: 2003
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/290295 , vital:56737 , xlink:href="https://doi.org/10.1016/j.microc.2003.08.002"
- Description: Electrochemical properties of novel, peripherally substituted zinc phthalocyanine complex, octa(4-methylphenylthio-) phthalocyaninatozinc(II) [ZnPc(SC6H4CH3)8] (1a) in DMF solution are presented. This complex showed five quasi-reversible/reversible, diffusion-controlled redox couples. Solution voltammetry of 1a showed little contrast with that of its alkythiol-derivative, octabutylthiophthalocyaninatozinc(II) [ZnPc(SC4H9)8] (1b) in that both thiol-substituents tend to show electron-withdrawing influence on the phthalocyanine ligands; complex 1a showing easier reduction and more difficult to oxidation when compared to 1b and other alkyl derivatives. The voltammetric features of the solid ultrathin films of 1a and 1b, immobilized on gold electrodes via the self-assembling technique, are also presented. Interestingly, the self-assembled films are stable and reproducible and provide good suppression to the following Faradaic processes; gold surface oxidation, solution ion species and underpotential deposition (UPD) of copper.
- Full Text:
- Date Issued: 2003
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