Analysis of the Magnetic Entropy in Oxygen Reduction Reactions Catalysed by Manganite Perovskites

Jose Gracia, Julen Munarriz, Victor Polo, Ryan Sharpe, Yunzhe Jiao, J. W.Hans Niemantsverdriet, Tingbin Lim

Research output: Contribution to journalArticle

9 Citations (Scopus)

Abstract

Manganese oxides with a half-metallic ground state are particularly active for oxygen reduction reactions (ORR). La0.67Sr0.33MnO3 (LSMO) perovskite is the archetypal example for compositions with a Curie temperature (TC) above room temperature and with a high intrinsic activity for the partial reduction of triplet-state O2. The ferromagnetic (FM) character of the superexchange interactions in LSMO facilitates both charge and spin transport below 370 K. Other than the enhanced electronic conductivity, the reduced spin entropy seems to be relevant in oxygen catalysis because the magnetic ordering extends to the surface. The sign of the exchange interactions determines the adsorption of the triplet oxygen molecule with its spin antiparallel to the FM catalysts. Based on the transition-state theory, we report that on LSMO, the hindrance resulting from the magnetic entropy for the initial reduction of O2 by two antiparallel electrons to diamagnetic intermediates (such H2O2) is minimum. On the other hand, the additional reduction of H2O2 to H2O, diamagnetic steps, prefers paramagnetic catalysts with higher magnetic entropy such as La0.4Sr0.6MnO3 to avoid spin accumulation.

Original languageEnglish
Pages (from-to)3358-3363
Number of pages6
JournalChemCatChem
Volume9
Issue number17
DOIs
Publication statusPublished - 8 Sep 2017

Keywords

  • density functional calculations
  • magnetism
  • oxygen
  • perovskite phases
  • thermodynamics

ASJC Scopus subject areas

  • Catalysis
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

Cite this

Gracia, J., Munarriz, J., Polo, V., Sharpe, R., Jiao, Y., Niemantsverdriet, J. W. H., & Lim, T. (2017). Analysis of the Magnetic Entropy in Oxygen Reduction Reactions Catalysed by Manganite Perovskites. ChemCatChem, 9(17), 3358-3363. https://doi.org/10.1002/cctc.201700302