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

Cristian Linares-Flores, Ramiro Arratia-Pérez, Desmond Macleod Carey

Research output: Contribution to journalArticle

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.

Original languageEnglish
Pages (from-to)2185-2194
Number of pages10
JournalChemical Papers
Volume71
Issue number11
DOIs
Publication statusPublished - 1 Nov 2017

Fingerprint

Chemical reactivity
Oxidation-Reduction
Catalyst activity
Hardness
Oxygen
Binding energy
Density functional theory
Molecules

Keywords

  • Chemical hardness
  • Intermolecular chemical hardness
  • Metallophthalocyanines
  • Nucleophilicity index

ASJC Scopus subject areas

  • Chemistry(all)
  • Biochemistry
  • Chemical Engineering(all)
  • Industrial and Manufacturing Engineering
  • Materials Chemistry

Cite this

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title = "Chemical reactivity descriptors evaluation for determining catalytic activity, redox potential, and oxygen binding of metallophthalocyanines",
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.",
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Chemical reactivity descriptors evaluation for determining catalytic activity, redox potential, and oxygen binding of metallophthalocyanines. / Linares-Flores, Cristian; Arratia-Pérez, Ramiro; Macleod Carey, Desmond.

In: Chemical Papers, Vol. 71, No. 11, 01.11.2017, p. 2185-2194.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Chemical reactivity descriptors evaluation for determining catalytic activity, redox potential, and oxygen binding of metallophthalocyanines

AU - Linares-Flores, Cristian

AU - Arratia-Pérez, Ramiro

AU - Macleod Carey, Desmond

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AB - 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.

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