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A-site Ca substitution optimizing SrCoO3-δ phase structure and B-site environment for efficient oxygen evolution.

DaiWei Zhang1, HongYuan Song1,2, XiaoLong Yang1

  • 1Faculty of Materials Science and Engineering, Kunming University of Science and Technology, Kunming, 650093, PR China. songhongyuan0227@outlook.com.

Dalton Transactions (Cambridge, England : 2003)
|March 30, 2026
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Summary

Calcium doping in SrCoO3-δ perovskite catalysts enhances oxygen evolution reaction (OER) performance by optimizing crystal structure and cobalt electronic environment. The orthorhombic phase, Sr0.5Ca0.5CoO3-δ, demonstrates superior OER activity and stability.

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Area of Science:

  • Materials Science
  • Electrochemistry
  • Catalysis

Background:

  • Strontium cobaltite (SrCoO3-δ) is a promising electrocatalyst for the oxygen evolution reaction (OER).
  • The influence of A-site ions on the B-site local environment and phase structure of perovskite electrocatalysts is underexplored.
  • Tuning the A-site composition is crucial for optimizing the performance of perovskite-based OER catalysts.

Purpose of the Study:

  • To investigate the effect of A-site calcium (Ca) doping on the crystal structure and electronic properties of SrCoO3-δ.
  • To explore the relationship between Ca-induced structural modifications and the oxygen evolution reaction (OER) performance.
  • To provide insights into the rational design of efficient perovskite electrocatalysts for OER.

Main Methods:

  • Synthesis of Sr1-xCaxCoO3-δ (SCxCO) catalysts with varying Ca content (x = 0-0.5) via a sol-gel method.
  • Characterization using X-ray diffraction (XRD) with Rietveld refinement, Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS).
  • Electrochemical evaluation of OER activity and stability in 1 M KOH solution.

Main Results:

  • Ca doping induced a phase transformation from hexagonal to orthorhombic structure in Sr1-xCaxCoO3-δ (x ≥ 0.3).
  • The orthorhombic Sr0.5Ca0.5CoO3-δ exhibited the best OER performance, with an overpotential of 336 mV at 10 mA cm⁻², which decreased by 41 mV after 1000 CV cycles.
  • Ca doping optimized the Co valence state, suppressed surface Sr enrichment, and promoted the formation of oxygen vacancies and surface CoOOH species.

Conclusions:

  • A-site Ca doping is an effective strategy to modulate the crystal structure and B-site Co environment in SrCoO3-δ perovskites.
  • The orthorhombic phase and optimized electronic structure resulting from Ca doping significantly enhance OER kinetics and stability.
  • This study offers valuable insights for designing high-performance perovskite electrocatalysts for the oxygen evolution reaction.