This study demonstrates the importance of considering lattice oxygen participation in understanding trends in the oxygen evolution reaction (OER) on ABO₃ (A = lanthanum or strontium, B = transition metal) perovskites. Using density functional theory, we show that the lattice oxygen mechanism (LOM) can lead to higher OER activity than the conventional adsorbate evolving mechanism (AEM) by minimizing the thermodynamically required overpotential. We also show that the OER activity volcano for AEM is universal for all perovskites, whereas that for LOM depends on the identity of the A cation in ABO₃. This explains experimental observations that perovskites such as Pr_0.5Ba_0.5CoO_3−δ and SrCoO_3−δ show higher OER activities than the conventionally predicted optimum compounds such as LaNiO₃ and SrCoO₃. Furthermore, we show that LOM is preferred to AEM in achieving bifunctional catalysts capable of promoting both OER and ORR. Using our overall activity volcano, we finally suggest several candidate materials that are predicted to be highly active for OER via LOM.

中文翻译：

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晶格氧参与在理解钙钛矿上氧析出反应趋势中的作用

这项研究证明了考虑晶格氧参与了解AB O ₃（A =镧或锶，B =过渡金属）钙钛矿上的氧逸出反应（OER）趋势的重要性。使用密度泛函理论，我们表明，通过使热力学所需的超电势最小化，晶格氧机理（LOM）可以导致比常规吸附物演化机理（AEM）更高的OER活性。我们还表明，对于所有钙钛矿，AEM的OER活性火山都是通用的，而LOM的火山取决于AB O _3中A阳离子的身份。。这解释了实验观察结果，与传统预测的最佳化合物（例如LaNiO ₃和SrCoO _3）相比，钙钛矿（例如Pr _0.5 Ba _0.5 CoO _3-δ和SrCoO _3-δ）显示出更高的OER活性。此外，我们表明，在获得能够同时促进OER和ORR的双功能催化剂方面，LOM优于AEM。最后，使用我们的整体活动火山，我们建议通过LOM对OER具有高活性的几种候选材料。