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Chemical Papers

, Volume 71, Issue 11, pp 2185–2194 | Cite as

Chemical reactivity descriptors evaluation for determining catalytic activity, redox potential, and oxygen binding of metallophthalocyanines

  • Cristian Linares-Flores
  • Ramiro Arratia-Pérez
  • Desmond MacLeod Carey
Original Paper

Abstract

In this article, we employed density functional theory calculation methods to determine the relationship between the chemical hardness (η), intermolecular chemical hardness (η DA), and nucleophilicity (N) chemical reactivity descriptors, as well as the energy of the occupied frontier orbitals (E a1g), and the electrocatalytic activity of different metallophthalocyanines [MPc’s with M=Cr(II), Mn(II), Fe(II), Co(I), Ni(II), and Cu(II)] for the oxygen reduction reaction. Our results suggest that η DA, N, and E a1g are appropriate parameters to estimate the electrocatalytic activity. On the other hand, the type of the metallic center determines the strength of the oxygen-binding energy, where a strong electronic interaction promotes the efficient electro-reduction of the dioxygen molecule, which is observed experimentally as a high catalytic activity.

Keywords

Metallophthalocyanines Chemical hardness Intermolecular chemical hardness Nucleophilicity index 

Notes

Acknowledgements

The authors thank the financial support of FONDECYT Grants 1131123, 1150629, 3150438 and INICIATIVA CIENTIFICA MILENIO Grant RC120001.

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Copyright information

© Institute of Chemistry, Slovak Academy of Sciences 2017

Authors and Affiliations

  1. 1.Facultad de Ingeniería, Instituto de Ciencias Químicas Aplicadas, Inorganic Chemistry and Molecular Materials CenterUniversidad Autónoma de ChileSan MiguelChile
  2. 2.Centro de Nanociencias Aplicadas (CENAP), Doctorado de Fisicoquímica MolecularUniversidad Andres BelloSantiagoChile

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