In this work, different alkali metal (Na or K)-doped manganese-based metal–organic framework (Mn-MOF) derivative materials were obtained from Mn-MIL-100 through ex situ posttreatment method, and their catalytic activities were studied by toluene oxidation. A series of characterization results (N₂ adsorption–desorption, X-ray absorption spectroscopy, temperature programmed O₂ desorption, etc.) showed that Na-doped Mn-MOF derivatives presented larger specific surface area, lower average manganese valence, and better adsorbed oxygen mobility, which displayed higher catalytic activity. Interestingly, both the addition of alkali metal and the introduction of water in the reaction atmosphere promoted the mineralization of toluene, as demonstrated by in situ diffuse reflectance infrared Fourier transform spectroscopy and thermal desorption-gas chromatography-mass spectrometry. Density functional theory calculations further confirmed that alkali metals and H₂O were conducive to the adsorption of toluene, benzyl alcohol, benzaldehyde, benzoic acid and O₂. This work provides new ideas for developing high-efficiency and water-promotion Mn-based materials for VOC control.

本工作以 Mn-MIL-100 为原料，通过非原位后处理方法获得了不同的碱金属（Na 或 K）掺杂锰基金属有机骨架（Mn-MOF）衍生物材料，并用甲苯研究了它们的催化活性。氧化。一系列表征结果（N ₂吸附-解吸、X 射线吸收光谱、程序升温 O ₂脱附等）表明，Na掺杂的Mn-MOF衍生物具有更大的比表面积、更低的平均锰价和更好的吸附氧迁移率，表现出更高的催化活性。有趣的是，碱金属的添加和反应气氛中水的引入都促进了甲苯的矿化，原位漫反射红外傅里叶变换光谱和热解吸-气相色谱-质谱法证明了这一点。密度泛函理论计算进一步证实碱金属和H ₂ O有利于甲苯、苯甲醇、苯甲醛、苯甲酸和O _2的吸附. 该工作为开发用于VOC控制的高效促水锰基材料提供了新思路。