Formation of oxygen radicals in 12CaO·7Al2O3: Instability of extraframework oxide ions and uptake of oxygen gas

Katsuro Hayashi, Satoru Matsuishi, Masahiro Hirano, Hideo Hosono

Research output: Contribution to journalArticle

52 Citations (Scopus)

Abstract

The thermodynamics and kinetics of oxygen radical formation in cages of a nanoporous crystal, 12CaO·7Al2O3, were examined during isothermal annealing in a dry oxygen atmosphere. The formation of oxygen radicals, O2- and O-, involves the outward diffusion of extraframework oxide ions, their oxidation by absorbed oxygen molecules to form O- and O2- at the surface, and subsequent inward diffusion of the oxygen radicals. The instability of the extraframework oxide ions provides the driving force for this process. Evaluating the radical formation enthalpy and entropy enabled us to determine the temperature and oxygen partial pressure dependences of equilibrium oxygen radical concentration. The rate-limiting process for the radical formation is not the surface reaction, but the total ionic diffusion process, in which the smaller diffusivity of O2- likely dominates the process.

Original languageEnglish
Pages (from-to)8920-8925
Number of pages6
JournalJournal of Physical Chemistry B
Volume108
Issue number26
DOIs
Publication statusPublished - Jul 1 2004
Externally publishedYes

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Oxides
Reactive Oxygen Species
Gases
Ions
Oxygen
oxides
oxygen
gases
ions
Isothermal annealing
Partial Pressure
Surface reactions
Entropy
Atmosphere
Thermodynamics
Partial pressure
Enthalpy
ionic diffusion
Oxidation
Crystals

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films
  • Materials Chemistry

Cite this

Formation of oxygen radicals in 12CaO·7Al2O3 : Instability of extraframework oxide ions and uptake of oxygen gas. / Hayashi, Katsuro; Matsuishi, Satoru; Hirano, Masahiro; Hosono, Hideo.

In: Journal of Physical Chemistry B, Vol. 108, No. 26, 01.07.2004, p. 8920-8925.

Research output: Contribution to journalArticle

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