Applications of polymerized metal tetra-amino phthalocyanines towards hydrogen peroxide detection
- Mashazi, Philani N, Togo, Chumunorwa, Limson, Janice L, Nyokong, Tebello
- Authors: Mashazi, Philani N , Togo, Chumunorwa , Limson, Janice L , Nyokong, Tebello
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/261840 , vital:53451 , xlink:href="https://doi.org/10.1142/S1088424610001994"
- Description: This work reports the use of metallo tetra-amino phthalocyanines (MTAPc, M = Co and Mn) polymer thin films on gold and glassy carbon electrode surfaces for the detection and monitoring of hydrogen peroxide (H2O2). The polymer-modified electrodes were characterized using electrochemical and microscopic-based methods. Atomic force microscopy (AFM) was used to study the bare and polymer-modified ITO surfaces. The electrocatalytic reduction of H2O2 with glassy carbon polymer-modified electrodes gave higher current densities compared to their gold counterparts. The electroanalytical properties of H2O2 were obtained using a real-time calibration curve of the amperometric determination in pH 7.4 aqueous solution. The limits of detection (LoD) of the polymer-modified electrodes towards electroreduction of H2O2 were of the order of 10–7 M, with high sensitivity ranging from 6.0–15.4 mA.mM-1.cm-2.
- Full Text:
- Date Issued: 2010
- Authors: Mashazi, Philani N , Togo, Chumunorwa , Limson, Janice L , Nyokong, Tebello
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/261840 , vital:53451 , xlink:href="https://doi.org/10.1142/S1088424610001994"
- Description: This work reports the use of metallo tetra-amino phthalocyanines (MTAPc, M = Co and Mn) polymer thin films on gold and glassy carbon electrode surfaces for the detection and monitoring of hydrogen peroxide (H2O2). The polymer-modified electrodes were characterized using electrochemical and microscopic-based methods. Atomic force microscopy (AFM) was used to study the bare and polymer-modified ITO surfaces. The electrocatalytic reduction of H2O2 with glassy carbon polymer-modified electrodes gave higher current densities compared to their gold counterparts. The electroanalytical properties of H2O2 were obtained using a real-time calibration curve of the amperometric determination in pH 7.4 aqueous solution. The limits of detection (LoD) of the polymer-modified electrodes towards electroreduction of H2O2 were of the order of 10–7 M, with high sensitivity ranging from 6.0–15.4 mA.mM-1.cm-2.
- Full Text:
- Date Issued: 2010
Electrochemical, spectroscopic and microscopic studies of new manganese phthalocyanine complexes in solution and as self-assembled monolayers on gold
- Coates, Megan, Antunes, Edith M, Nyokong, Tebello
- Authors: Coates, Megan , Antunes, Edith M , Nyokong, Tebello
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/261144 , vital:53363 , xlink:href="https://doi.org/10.1142/S1088424610002471"
- Description: Four new manganese(III) phthalocyanines (3a–d), octasubstituted at the peripheral position with pentylthio, decylthio, benzylthio, and phenylthio groups, respectively, were synthesized. Their specific electrochemical, spectroscopic and microscopic properties in solution and as self-assembled monolayers on gold were characterized. The UV-vis spectra confirmed red-shifted Q bands for all the complexes, due to the effect of the central metal and the electron-donating substituents. Three redox couples were visible during cyclic voltammetry studies for the four complexes, and spectroelectrochemistry confirmed the couples as corresponding to MnIIIPc-2/MnIIPc-2 (II) (metal reduction), MnIIPc-2/MnIIPc-3 (III) (ring reduction) and MnIIIPc-1/MnIIIPc-2 (I) (ring oxidation). Electrochemistry was also used to determine the blocking characteristics of the MnPc self-assembled monolayers on gold, which proved to be highly dependent on the type of substituent. Other methods of characterization included Raman spectroscopy, atomic force and scanning electrochemical microscopy analyses of the SAMs.
- Full Text:
- Date Issued: 2010
- Authors: Coates, Megan , Antunes, Edith M , Nyokong, Tebello
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/261144 , vital:53363 , xlink:href="https://doi.org/10.1142/S1088424610002471"
- Description: Four new manganese(III) phthalocyanines (3a–d), octasubstituted at the peripheral position with pentylthio, decylthio, benzylthio, and phenylthio groups, respectively, were synthesized. Their specific electrochemical, spectroscopic and microscopic properties in solution and as self-assembled monolayers on gold were characterized. The UV-vis spectra confirmed red-shifted Q bands for all the complexes, due to the effect of the central metal and the electron-donating substituents. Three redox couples were visible during cyclic voltammetry studies for the four complexes, and spectroelectrochemistry confirmed the couples as corresponding to MnIIIPc-2/MnIIPc-2 (II) (metal reduction), MnIIPc-2/MnIIPc-3 (III) (ring reduction) and MnIIIPc-1/MnIIIPc-2 (I) (ring oxidation). Electrochemistry was also used to determine the blocking characteristics of the MnPc self-assembled monolayers on gold, which proved to be highly dependent on the type of substituent. Other methods of characterization included Raman spectroscopy, atomic force and scanning electrochemical microscopy analyses of the SAMs.
- Full Text:
- Date Issued: 2010
Photoelectrochemical characterization of electrodeposited ZnO thin films sensitized by octacarboxymetallophthalocyanine derivatives
- Idowu, Mopelola, Loewenstein, Thomas, Hastall, Andreas, Nyokong, Tebello, Schlettwein, Derck
- Authors: Idowu, Mopelola , Loewenstein, Thomas , Hastall, Andreas , Nyokong, Tebello , Schlettwein, Derck
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/262655 , vital:53541 , xlink:href="https://doi.org/10.1142/S1088424610001854"
- Description: Hybrid thin films of crystalline zinc oxide (ZnO) modified by different octacarboxymetallophthalocyanines (MOCPc) were prepared by the readsorption method. Homogeneously blue or green thin films were formed. The photoelectrochemical characteristics of the electrodes were studied by time-resolved photocurrent measurements. Zinc(II) 2,3,9,10,16,17,23,24-octacarboxyphthalocyanine (ZnOCPc) showed considerably large quantum efficiency in sensitization of ZnO, one of the highest quantum efficiencies obtained so far with phthalocyanine-type sensitizers on nanocrystalline ZnO films.
- Full Text:
- Date Issued: 2010
- Authors: Idowu, Mopelola , Loewenstein, Thomas , Hastall, Andreas , Nyokong, Tebello , Schlettwein, Derck
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/262655 , vital:53541 , xlink:href="https://doi.org/10.1142/S1088424610001854"
- Description: Hybrid thin films of crystalline zinc oxide (ZnO) modified by different octacarboxymetallophthalocyanines (MOCPc) were prepared by the readsorption method. Homogeneously blue or green thin films were formed. The photoelectrochemical characteristics of the electrodes were studied by time-resolved photocurrent measurements. Zinc(II) 2,3,9,10,16,17,23,24-octacarboxyphthalocyanine (ZnOCPc) showed considerably large quantum efficiency in sensitization of ZnO, one of the highest quantum efficiencies obtained so far with phthalocyanine-type sensitizers on nanocrystalline ZnO films.
- Full Text:
- Date Issued: 2010
Probing electrochemical and electrocatalytic properties of cobalt (II) and manganese (III) octakis (hexylthio) phthalocyanine as self-assembled monolayers
- Mashazi, Philani N, Antunes, Edith M, Nyokong, Tebello
- Authors: Mashazi, Philani N , Antunes, Edith M , Nyokong, Tebello
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/249115 , vital:51779 , xlink:href="https://doi.org/10.1142/S108842461000277X"
- Description: New peripherally (β) and non-peripherally (α) substituted metal octakis(hexylthio)phthalocyanines (β- and α-MOcHexTPc) containing cobalt and manganese as metal centers were synthesized. Their characterization using electrochemical methods showed that these complexes exhibit several redox processes at E1/2 (mV vs. Ag∣AgCl) = 380 (212) (I), 1140 (864) (II), -450 (-460) (III) and -1170 (-1304) (IV) for β- (α-) CoOcHexTPc. These redox processes were assigned to CoIIIPc-2/CoIIPc-2 (I), CoIIIPc-1/CoIIIPc-2 (II), CoIIPc-2/CoIPc-2 (III) and CoIPc-2/CoIPc-3 (IV) using spectroelectrochemistry. For the β- (α-) MnOcHexTPc complex the redox processes were observed at E1/2 (mV vs. Ag∣AgCl) = -20 (5) (I), -530 (-640) (II) and -1270 (-1380) (III) and were assigned to MnIIIPc-2/MnIIPc-2 (I), MnIIPc-2/MnIIPc-3 (II) and MnIIPc-3/MnIIPc-4 (III). Electrochemical and microscopic characterization using AFM showed that the self-assembled monolayers (SAMs) are formed on the gold surface using these complexes. The electrochemical characterization showed the blocking of the Faradaic processes at SAMs modified electrodes and these reactions are well-known to easily occur at unmodified gold electrodes. The AFM characterization showed an increase in surface roughness upon modifying the gold surface with MOcHexTPc SAMs, further confirming the presence of the monolayers on the gold surface. The MOcHexTPc SAMs were investigated for their electrocatalytic application towards H2O2 detection. The MOcHexTPc SAMs modified gold electrodes gave excellent currents for H2O2 detection. The observed H2O2 electrocatalytic reduction peaks were close to where the metal redox processes from the MOcHexTPc occurred, showing the involvement of the metal redox processes in the electrocatalytic mediation reactions.
- Full Text:
- Date Issued: 2010
- Authors: Mashazi, Philani N , Antunes, Edith M , Nyokong, Tebello
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/249115 , vital:51779 , xlink:href="https://doi.org/10.1142/S108842461000277X"
- Description: New peripherally (β) and non-peripherally (α) substituted metal octakis(hexylthio)phthalocyanines (β- and α-MOcHexTPc) containing cobalt and manganese as metal centers were synthesized. Their characterization using electrochemical methods showed that these complexes exhibit several redox processes at E1/2 (mV vs. Ag∣AgCl) = 380 (212) (I), 1140 (864) (II), -450 (-460) (III) and -1170 (-1304) (IV) for β- (α-) CoOcHexTPc. These redox processes were assigned to CoIIIPc-2/CoIIPc-2 (I), CoIIIPc-1/CoIIIPc-2 (II), CoIIPc-2/CoIPc-2 (III) and CoIPc-2/CoIPc-3 (IV) using spectroelectrochemistry. For the β- (α-) MnOcHexTPc complex the redox processes were observed at E1/2 (mV vs. Ag∣AgCl) = -20 (5) (I), -530 (-640) (II) and -1270 (-1380) (III) and were assigned to MnIIIPc-2/MnIIPc-2 (I), MnIIPc-2/MnIIPc-3 (II) and MnIIPc-3/MnIIPc-4 (III). Electrochemical and microscopic characterization using AFM showed that the self-assembled monolayers (SAMs) are formed on the gold surface using these complexes. The electrochemical characterization showed the blocking of the Faradaic processes at SAMs modified electrodes and these reactions are well-known to easily occur at unmodified gold electrodes. The AFM characterization showed an increase in surface roughness upon modifying the gold surface with MOcHexTPc SAMs, further confirming the presence of the monolayers on the gold surface. The MOcHexTPc SAMs were investigated for their electrocatalytic application towards H2O2 detection. The MOcHexTPc SAMs modified gold electrodes gave excellent currents for H2O2 detection. The observed H2O2 electrocatalytic reduction peaks were close to where the metal redox processes from the MOcHexTPc occurred, showing the involvement of the metal redox processes in the electrocatalytic mediation reactions.
- Full Text:
- Date Issued: 2010
Symmetrically and unsymmetrically substituted carboxy phthalocyanines as sensitizers for nanoporous ZnO films
- Masilela, Nkosiphile, Nombona, Nolwazi, Loewenstein, Thomas, Nyokong, Tebello, Schlettwein, Derck
- Authors: Masilela, Nkosiphile , Nombona, Nolwazi , Loewenstein, Thomas , Nyokong, Tebello , Schlettwein, Derck
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/249126 , vital:51780 , xlink:href="https://doi.org/10.1142/S1088424610002793"
- Description: The photoelectroectrochemical studies of water soluble octacarboxylated oxotitanium (OTiOCPc), zinc (ZnOCPC), hydroxyaluminium ((OH)AlOCPc), dihydroxysilicon ((OH)2SiOCPc), hydroxygallium (OHGaOCPc) and low symmetry zinc monocarboxy (ZnMCPc) phthalocyanines were performed. The dyes were adsorbed to nanoporous ZnO electrodeposited in the presence of eosin Y as structure directing agent (SDA) on FTO substrates by refluxing or soaking the films in a solution containing the dye of interest such that a full surface coverage was achieved. High external (IPCE) and internal (APCE) quantum efficiencies of up to 50.6% and 96.7% were achieved for the OTiOCPc complex. There was a lower overall cell efficiency for cells sensitized with phthalocyanines containing hydroxyl as axial ligand ZnO/(OH)2SiOCPc, ZnO/(OH)GaOCPc and (OH)AlOCPc because of strong aggregation on the surface of the electrodes. To further suppress dye aggregation, the zinc complex of a new monocarboxylated phthalocyanine sensitizer with bulky naphtho side groups (ZnMCPc) was employed. Among the studied sensitizers, ZnMCPc gave the highest overall cell efficiency of phthalocyanine electrodeposited on ZnO of η = 0.48%.
- Full Text:
- Date Issued: 2010
- Authors: Masilela, Nkosiphile , Nombona, Nolwazi , Loewenstein, Thomas , Nyokong, Tebello , Schlettwein, Derck
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/249126 , vital:51780 , xlink:href="https://doi.org/10.1142/S1088424610002793"
- Description: The photoelectroectrochemical studies of water soluble octacarboxylated oxotitanium (OTiOCPc), zinc (ZnOCPC), hydroxyaluminium ((OH)AlOCPc), dihydroxysilicon ((OH)2SiOCPc), hydroxygallium (OHGaOCPc) and low symmetry zinc monocarboxy (ZnMCPc) phthalocyanines were performed. The dyes were adsorbed to nanoporous ZnO electrodeposited in the presence of eosin Y as structure directing agent (SDA) on FTO substrates by refluxing or soaking the films in a solution containing the dye of interest such that a full surface coverage was achieved. High external (IPCE) and internal (APCE) quantum efficiencies of up to 50.6% and 96.7% were achieved for the OTiOCPc complex. There was a lower overall cell efficiency for cells sensitized with phthalocyanines containing hydroxyl as axial ligand ZnO/(OH)2SiOCPc, ZnO/(OH)GaOCPc and (OH)AlOCPc because of strong aggregation on the surface of the electrodes. To further suppress dye aggregation, the zinc complex of a new monocarboxylated phthalocyanine sensitizer with bulky naphtho side groups (ZnMCPc) was employed. Among the studied sensitizers, ZnMCPc gave the highest overall cell efficiency of phthalocyanine electrodeposited on ZnO of η = 0.48%.
- Full Text:
- Date Issued: 2010
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