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Exceptional oxygen evolution reactivities on CaCoO3 and SrCoO3.

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CaCoO3 and SrCoO3 exhibit similar catalytic onset potentials for the oxygen evolution reaction (OER). However, CaCoO3 demonstrates enhanced stability and activity due to its smaller lattice parameter and reduced surface oxygen separation.

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Area of Science:

  • Materials Science
  • Electrochemistry
  • Catalysis

Background:

  • The oxygen evolution reaction (OER) is crucial for energy conversion technologies.
  • Transition metal oxides are promising OER electrocatalysts.
  • Understanding structure-activity relationships is key to designing efficient catalysts.

Purpose of the Study:

  • To investigate the influence of covalent bonding, surface oxygen separation, and electrolyte pH on OER.
  • To compare the catalytic performance of CaCoO3 and SrCoO3 for OER.
  • To elucidate the surface reaction mechanisms governing OER activity.

Main Methods:

  • Comparative study of CaCoO3 and SrCoO3 perovskites.
  • Analysis of catalytic onset potentials and OER activity.
  • Investigation of surface reaction pathways.

Main Results:

  • Both CaCoO3 and SrCoO3 are cubic, metallic perovskites with similar Co(IV) intermediate spin states and onset potentials.
  • CaCoO3 exhibits a smaller lattice parameter and shorter surface oxygen separation.
  • CaCoO3 demonstrates increased OER stability and activity compared to SrCoO3.

Conclusions:

  • Surface oxygen separation significantly impacts OER activity.
  • A smaller surface oxygen separation favors a faster OER pathway involving peroxide formation and oxygen vacancy attack.
  • CaCoO3 is a more stable and active OER catalyst due to its optimized surface structure.