Density functional theory is employed to investigate the electronic origin and feasibility of surface lattice oxygen (O_surf) participation during the oxygen evolution reaction (OER) on perovskites. O_surf participation occurs via the nonelectrochemical pathway in which adsorbed atomic oxygen (O*) diffuses from the transition-metal site to the oxygen site, and then O_surf shifts out of the surface plane to react with O* to form O_surf–O* and a surface oxygen vacancy. The different thermodynamic driving forces of O_surf participation on LaMO_3−δ (M = Ni, Co, and Cu) are explained by the changes in the oxidation state of the transition-metal site throughout the reaction. We show that O_surf participation on LaNiO₃ cannot be hindered by O_surf protonation in the OER potential range. By including the coverage effect and utilizing the implicit solvent model, we finally show that lattice oxygen mechanism is more feasible than the conventional mechanism for OER on LaNiO₃.

中文翻译：

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钙钛矿上析氧反应过程中晶格氧参与的电子起源和动力学可行性

密度泛函理论用于研究钙钛矿上氧析出反应（OER）过程中表面晶格氧（O _surf）参与的电子起源和可行性。O _surf的参与通过非电化学途径发生，其中吸附的原子氧（O *）从过渡金属部位扩散到氧部位，然后O _surf移出表面，与O *反应形成O _surf –O *和表面氧空位。O _surf参与LaMO3 _-δ的不同热力学驱动力（M = Ni，Co和Cu）可以通过整个反应过程中过渡金属位点的氧化态变化来解释。我们证明O_冲浪上的LaNiO参与₃不能被O受阻_冲浪质子化的OER电位范围。通过包括覆盖效应并利用隐式溶剂模型，我们最终证明晶格氧机制比常规的LaNiO ₃上OER的机制更可行。