Developing RuO-based electrocatalysts with high activity and stability for acidic oxygen evolution reaction (OER) is highly desirable but remains a challenge. More critically, strategies for rational manipulation of the reaction pathway of RuO from a kinetically favorable but unstable lattice oxygen oxidation mechanism (LOM) pathway to an adsorption evolution mechanism (AEM) pathway are still elusive. Herein, we report the synthesis of Ce-doped RuO catalysts with the existence of oxygen vacancies (Ce-RuO). Experimental results and density functional theory (DFT) calculations reveal that Ru valence state is lowered with the formation of Ce-O-Ru local structure, and Ru-O covalency is decreased, which suppress the surface Ru demetallation and lattice oxygen loss, resulting in greatly enhanced durability toward acidic OER. Moreover, the synergistic effect between Ce-O-Ru local structure and oxygen vacancies can be conducive to the stabilization of OOH∗, leading to a manipulated reaction pathway from LOM to AEM and reduced energy barrier of the rate-determining step.

中文翻译：

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操纵氧化钌的反应途径，增强酸性水氧化的性能和稳定性


开发用于酸性析氧反应（OER）的具有高活性和稳定性的 RuO 基电催化剂是非常理想的，但仍然是一个挑战。更关键的是，合理控制 RuO 反应路径从动力学有利但不稳定的晶格氧氧化机制 (LOM) 路径到吸附演化机制 (AEM) 路径的策略仍然难以捉摸。在此，我们报道了存在氧空位的 Ce 掺杂 RuO 催化剂（Ce-RuO）的合成。实验结果和密度泛函理论（DFT）计算表明，Ru价态随着Ce-O-Ru局域结构的形成而降低，Ru-O共价性降低，抑制了表面Ru脱金属和晶格氧损失，从而导致大大增强了对酸性OER的耐受性。此外，Ce-O-Ru局域结构和氧空位之间的协同效应有利于OOH*的稳定，从而控制从LOM到AEM的反应路径，并降低速率决定步骤的能垒。