Tuning the redox properties of metalloporphyrin-and metallophthalocyanine-based molecular electrodes for the highest electrocatalytic activity in the oxidation of thiols

Bedioui, Fethi; Griveau, Sophie; Caro, Claudia A; Gulppi, Miguel; Ochoa, Gonzalo; Zagal, José H

Title: Tuning the redox properties of metalloporphyrin-and metallophthalocyanine-based molecular electrodes for the highest electrocatalytic activity in the oxidation of thiols
Creator: Bedioui, Fethi
Creator: Griveau, Sophie
Creator: Nyokong, Tebello
Creator: Appleby, A John
Creator: Caro, Claudia A
Creator: Gulppi, Miguel
Creator: Ochoa, Gonzalo
Creator: Zagal, José H
Subject: To be catalogued
Date Issued: 2007
Date: 2007
Type: text
Type: article
Identifier: http://hdl.handle.net/10962/283988
Identifier: vital:56009
Identifier: xlink:href="https://doi.org/10.1039/B618767F"
Description: In this work we discuss different approaches for achieving electrodes modified with N4 macrocyclic complexes for the catalysis of the electrochemical oxidation of thiols. These approaches involve adsorption, electropolymerization and molecular anchoring using self assembled monolayers. We also discuss the parameters that determine the reactivity of these complexes. Catalytic activity is associated with the nature of the central metal, redox potentials and Hammett parameters of substituents on the ligand. Correlations between catalytic activity (log i at constant E) and the redox potential of catalysts for complexes of Cr, Mn, Fe, Co, Ni and Cu are linear with an increase of activity for more positive redox potentials. For a great variety complexes bearing the same metal center (Co) correlations between log i and Eo′ of the Co(II)/Co(I) couple have the shape of an unsymmetric volcano. This indicates that the potential of the Co(II)/Co(I) couple can be tuned using the appropiate ligand to achieve maximum catalytic activity. Maximum activity probably corresponds to a ΔG of adsorption of the thiol on the Co center equal to zero, and to a coverage of active sites by the thiol equal to 0.5.
Format: computer
Format: online resource
Format: application/pdf
Format: 1 online resource (14 pages)
Format: pdf
Publisher: Royal Society of Chemistry
Language: English
Relation: Physical Chemistry Chemical Physics
Relation: Bedioui, F., Griveau, S., Nyokong, T., Appleby, A.J., Caro, C.A., Gulppi, M., Ochoa, G. and Zagal, J.H., 2007. Tuning the redox properties of metalloporphyrin-and metallophthalocyanine-based molecular electrodes for the highest electrocatalytic activity in the oxidation of thiols. Physical Chemistry Chemical Physics, 9(26), pp.3383-3396
Relation: Physical Chemistry Chemical Physics volume 9 number 26 p. 3383 2007 1463-9076
Rights: Publisher
Rights: Use of this resource is governed by the terms and conditions of the Royal Society of Chemistry Terms and Conditions Statement (https://0-www.rsc.org.wam.seals.ac.za/help-legal/)
Rights: Open Access

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RU DST/NRF SARChI for Medicinal Chemistry and Nanotechnology

Nyokong, Tebello (Distinguished Professor)

RU Department of Chemistry

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