In this study, alkali metal and alkaline earth metal perovskites have been synthesized using simple preparation methods for catalyzing the oxidative coupling of methane (OCM) and oxidative dehydrogenation of ethane (ODHE). The influence of their structural parameters (such as tolerance factor t, unit cell free volume (V_f), electronegativity of A- and B-site elements, average metal-oxygen energy, and crystalline phase transition) on basic sites and reaction performance is also systematically investigated. The results show that these two perovskites have similar active sites for OCM and ODHE reactions, with the moderate and strong basic sites favoring the OCM reaction and the moderate basic site facilitating the ODHE reaction. The surface basicity of these perovskites reflects the electron-donating ability of lattice oxygen, which in turn affects the production of reactive oxygen species (O₂⁻, O₂²⁻, and O⁻). Moderate basic sites are abundant and closely related to oxygen vacancies, with high oxygen vacancy concentrations generating abundant reactive oxygen species. Meanwhile, V_f values of perovskites govern the CH₄, C₂H₆, and O₂ conversions, the electronegativity of elements affects the catalyst basicity, and the average metal-oxygen energy and crystalline phase transition alter the moderate basic sites. Overall, it concludes that perovskites should meet the following conditions to achieve excellent catalytic performance for OCM and ODHE: moderate V_f, low electronegativity of A- and B-site elements, low average metal oxygen energy, and a crystalline structure that changes with temperature.

本研究采用简单的制备方法合成了碱金属和碱土金属钙钛矿，用于催化甲烷氧化偶联（OCM）和乙烷氧化脱氢（ODHE）。其结构参数（如容差因子t、晶胞自由体积（V _f）、A位和B位元素的电负性、平均金属氧能和结晶相变）以及碱性位点上的反应性能也得到了系统的研究。结果表明，这两种钙钛矿具有相似的OCM和ODHE反应活性位点，中碱性位点和强碱性位点有利于OCM反应，中碱性位点有利于ODHE反应。这些钙钛矿的表面碱度反映了晶格氧的给电子能力，进而影响活性氧物种（O ₂ ⁻、O ₂ ²⁻和 O ^{− ）的产生。}）。中碱性位点丰富且与氧空位密切相关，高氧空位浓度会产生丰富的活性氧。同时，钙钛矿的V _f值控制CH ₄、C ₂ H ₆和O ₂转化，元素的电负性影响催化剂的碱性，平均金属-氧能和结晶相变改变中等碱性位点。总的来说，钙钛矿应满足以下条件才能实现 OCM 和 ODHE 的优异催化性能：适中的 V _f、A位和B位元素的低电负性、低平均金属氧能以及随温度变化的晶体结构。