Journal
ELECTROCHIMICA ACTA
Volume 46, Issue 20-21, Pages 3227-3235Publisher
PERGAMON-ELSEVIER SCIENCE LTD
DOI: 10.1016/S0013-4686(01)00614-4
Keywords
metallophthatocyanines; modified electrodes; O-2 reduction; 2-mercaptoethanol oxidation; Hammett parameters; donor-acceptor intermolecular hardness
Categories
Ask authors/readers for more resources
We have carried out a systematic study of the electrocatalytic activity of metallophthalocyanines (M(II)-Pcs) adsorbed on graphite electrodes for the electro-oxidation of thiols (R-SH) and for the electroreduction of molecular oxygen. We have found for both reactions that when comparing the activity of substituted phthalocyanines of the same metal, plots of log k at constant potential versus the redox potential of the metallophthalocyanine, the rate of the reaction decreases with increasing driving force of the catalyst. In this work we present evidence that this behavior can be rationalized in terms of the donor-acceptor intermolecular chemical hardness (eta (DA)). The energies of frontier orbitals involved in the estimation of eta (DA) were calculated using the PM3 semi-empirical theoretical method. For the donor-acceptor pairs the lower is the hardness, the higher is the reactivity. (C) 2001 Elsevier Science Ltd. All rights reserved.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available