We reported a detailed mechanistic study of the oxygen reduction reaction (ORR) on the model Ag(111) surface in alkaline solution by using density functional theory (DFT) and Kinetic Monte Carlo (KMC) simulations, in which multiple pathways involving either 2 e⁻ or 4 e⁻ mechanisms were included. The theoretical modelling presented is able to reproduce the experimentally measured polarization curves in both low and high potential regions. An electrochemical 4 e⁻ network including both a chemisorbed water (*H₂O)‐mediated 4 e⁻ associative pathway and the conventional associative pathway was identified to dominate the ORR mechanism. On the basis of the mechanistic understanding derived from these calculations, the ways to promote the ORR on Ag(111) were provided, including facilitating *OH removal, **O₂ reduction by *H₂O, and suppressing **O₂ desorption. Finally, the origin of the different ORR behaviors of Ag(111) and Pt(111) was also discussed in detail.

中文翻译：

---

碱性溶液中Ag（111）上的氧还原反应：密度泛函理论和动力学蒙特卡洛研究的结合

我们报告了使用密度泛函理论（DFT）和动力学蒙特卡洛（KMC）模拟的碱性溶液中模型Ag（111）表面上的氧还原反应（ORR）的详细机理研究，其中多个途径涉及2 e ^-或4个E ^-机制都包括在内。提出的理论模型能够在低和高电势区域中重现实验测得的极化曲线。一种电化学4 E ^-网络既包括化学吸附的水（* H ₂ O） -介导的4 E ^-关联途径和常规的关联途径被确定为主导ORR机制。根据从这些计算得出的机理理解，提供了促进在Ag（111）上进行ORR的方法，包括促进* OH去除，** O ₂被* H ₂ O还原和抑制** O ₂解吸的方法。 。最后，还详细讨论了Ag（111）和Pt（111）不同ORR行为的起源。