The first selective oxidation of methane to methanol is reported herein for zinc‐exchanged MOR (Zn/MOR). Under identical conditions, Zn/FER and Zn/ZSM‐5 both form zinc formate and methanol. Selective methane activation to form [Zn‐CH₃]⁺ species was confirmed by ¹³C MAS NMR spectroscopy for all three frameworks. The percentage of active zinc sites, measured through quantitative NMR spectroscopy studies, varied with the zeolite framework and was found to be ZSM‐5 (5.7 %), MOR (1.2 %) and FER (0.5 %). For Zn/MOR, two signals were observed in the ¹³C MAS NMR spectrum, resulting from two distinct [Zn‐CH₃]⁺ species present in the 12 MR and 8 MR side pockets, as supported by additional NMR experiments. The observed products of oxidation of the [Zn‐CH₃]⁺ species are shown to depend on the zeolite framework type and the oxidative conditions used. These results lay the foundation for developing structure–function correlations for methane conversion over zinc‐exchanged zeolites.

中文翻译：

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框架对锌交换沸石中甲烷活化和功能化的影响。

对于锌交换的MOR（Zn / MOR），据报道甲烷首次选择性氧化为甲醇。在相同条件下，Zn / FER和Zn / ZSM-5均会形成甲酸锌和甲醇。通过所有三个框架的¹³ C MAS NMR光谱证实了选择性甲烷活化形成[Zn-CH ₃ ] ⁺物种。通过定量NMR光谱研究测量的活性锌位点的百分比随沸石骨架的变化而变化，被发现为ZSM-5（5.7％），MOR（1.2％）和FER（0.5％）。对于Zn / MOR，在¹³ C MAS NMR光谱中观察到两个信号，这是由于两个不同的[Zn-CH ₃ ] ⁺在其他NMR实验的支持下，存在于12个MR和8 MR侧袋中的其他物种。观察到的[Zn-CH ₃ ] ⁺物种的氧化产物取决于沸石骨架类型和所使用的氧化条件。这些结果为开发锌交换沸石上甲烷转化的结构-功能相关性奠定了基础。