In this work, we develop a new microkinetic model for the oxygen reduction reaction (ORR) which incorporates field effects into the established computational hydrogen electrode model. We find that the field can significantly alter the binding energy of ORR adsorbates, particularly *OOH, *O₂, and *H₂O₂. By considering these effects, we find that the model gives polarization curves and rotating ring disk electrode currents consistent with those found experimentally on the Pt(111), Au(111), and Au(100) electrodes, allowing us to predict onset potentials for both overall ORR activity and activity toward hydrogen peroxide as well as reproduce experimental Tafel slopes. In particular, we resolve the peculiar behavior observed on the Au(100) surface, where increasing pH leads to greatly enhanced 4e-ORR activity, without strongly affecting 2e-ORR activity. We then use these predictions to better understand activity across all ORR catalysts, showing that weak-binding catalysts are more influenced by pH because of the strong field effects on the *OOH adsorbate. Finally, we argue that considering field effects can expand the search for improved ORR catalysts by allowing us to deconvolute the activity dependence of catalysts on the standard hydrogen electrode and the reversible hydrogen electrode.

中文翻译：

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氧还原动力学中的电场效应：合理化Pt（111），Au（111）和Au（100）电极的pH依赖性

在这项工作中，我们为氧还原反应（ORR）开发了一种新的微动力学模型，该模型将场效应纳入了已建立的计算氢电极模型中。我们发现该场可以显着改变ORR吸附物的结合能，特别是* OOH，* O ₂和* H ₂ O ₂。通过考虑这些影响，我们发现该模型给出的极化曲线和旋转环盘电极电流与在Pt（111），Au（111）和Au（100）电极上实验发现的一致，从而使我们能够预测总体ORR活性和对过氧化氢的活性，以及​​重现实验的Tafel斜率。特别是，我们解决了在Au（100）表面观察到的特殊行为，在此行为中，pH值的增加会导致4e-ORR活性大大增强，而不会强烈影响2e-ORR活性。然后，我们使用这些预测来更好地了解所有ORR催化剂的活性，这表明弱结合催化剂受* OOH吸附物的强场效应的影响更大。最后，