Herein, we attempted to identify the active sites behavior of perovskite catalysts in the oxidative coupling of methane (OCM) reaction, using ten types of ABO₃ perovskite catalysts with different structural properties according to their A and B site elements. The results showed that the catalyst surface lattice oxygen species are responsible for the selective conversion of methane. In particular, surface lattice oxygen species with moderate binding energies selectively catalyzed the OCM to produce C₂ hydrocarbons. The surface oxygen vacancies, resulting from the reaction of lattice oxygen and CH₄, were refilled with adsorbed surface oxygen and bulk lattice oxygen species. This oxygen cycle was closely related to the oxygen ion conductivity of perovskites, which could be determined based on their structural factors, such as the tolerance factor and the specific free volume. Accordingly, a facile oxygen cycle resulted in a high CH₄ conversion during this reaction. Finally, we concluded that the lattice oxygen properties and the oxygen ion conductivity of perovskite catalysts are key factors in determining the catalytic activity and should, therefore, be precisely controlled for the systematic design of efficient OCM catalysts.

本文中，我们尝试根据十种类型的ABO ₃钙钛矿催化剂的A和B位点元素，使用十种结构特征不同的ABO ₃钙钛矿催化剂来确定钙钛矿催化剂在甲烷氧化偶联（OCM）反应中的活性位点行为。结果表明，催化剂表面晶格中的氧是甲烷选择性转化的原因。特别地，具有中等结合能的表面晶格氧物种选择性地催化OCM以产生C ₂烃。由晶格氧与CH ₄反应产生的表面氧空位用吸附的表面氧和块状氧再填充。该氧循环与钙钛矿的氧离子电导率密切相关，这可以根据钙钛矿的结构因素，如耐受性因素和比自由体积来确定。因此，在该反应期间，容易的氧循环导致高的CH ₄转化率。最后，我们得出结论，钙钛矿型催化剂的晶格氧性质和氧离子电导率是决定催化活性的关键因素，因此，对于有效的OCM催化剂的系统设计，应对其进行精确控制。