Density functional theory calculations were employed to investigate the electrochemical oxygen reduction reaction on the (111) and (100) surfaces of cobalt(II) oxide. Different mechanisms were applied to evaluate the oxygen reduction reaction performance of cobalt(II) oxide structures in terms of the Gibbs free energy and density of states. A variety of intermediate structures based on associative and dissociative mechanisms were constructed and optimized. As a result, we estimated the catalytic activity by calculating the free energy of the intermediates and constructing free energy diagrams, which suggested that the oxygen reduction reaction Gibbs free energy on cobalt(II) oxide (111) and (100) surfaces based on the associative mechanism is smaller than that based on the dissociative mechanism, demonstrating that the associative mechanism should be more likely to be the oxygen reduction reaction pathway. Moreover, the theoretical oxygen reduction reaction activity on the cobalt(II) oxide (111) surface was found to be higher than that on the cobalt(II) oxide (100) surface. These results shed light on the rational design of high-performance cobalt(II) oxide oxygen reduction reaction catalysts.

中文翻译：

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氧化钴 (II) (111) 和 (100) 表面氧还原反应的密度泛函理论研究

采用密度泛函理论计算来研究氧化钴 (II) 的 (111) 和 (100) 表面上的电化学氧还原反应。根据吉布斯自由能和态密度，应用不同的机制来评估氧化钴 (II) 结构的氧还原反应性能。构建并优化了多种基于结合和解离机制的中间结构。因此，我们通过计算中间体的自由能并构建自由能图来估计催化活性，这表明基于氧化钴（II）（111）和（100）表面的氧还原反应吉布斯自由能结合机制比基于解离机制的要小，证明缔合机制更可能是氧还原反应途径。此外，发现氧化钴（II）（111）表面的理论氧还原反应活性高于氧化钴（II）（100）表面的理论氧还原反应活性。这些结果阐明了高性能氧化钴（II）氧还原反应催化剂的合理设计。