The production of acetic acid, an important industrial chemical traditionally obtained through the carbonylation of methanol using noble metal‐based homogeneous catalysts, encounters challenges arising from high equipment costs and sustainability concerns. The direct liquid‐phase oxidative carbonylation of methane emerges as a promising alternative, capitalizing on abundant natural gas resources and featuring a potentially mild and straightforward process. However, most catalysts proposed for this process suffer from low acetic acid yields due to the scarcity of active sites and the swift generation of C1 oxygenates, posing difficulties for subsequent carbonylation and impeding their industrial feasibility. Herein, we report a highly efficient 0.1Cu/Fe‐HZ5‐TF catalyst featuring exclusively mononuclear Fe and Cu anchored in the ZSM‐5 channels. Under optimized conditions, the catalyst achieved an unprecedented acetic acid yield of 40.5 mmol gcat‐1 h‐1 at 50 °C, surpassing the previous maximum (12.0 mmol gcat‐1h‐1) by more than threefold. Comprehensive characterization, isotope‐labeled experiments and DFT calculations reveal that the homogeneous mononuclear Fe sites are responsible for the activation and oxidation of methane, while the neighboring Cu sites play a key role in retarding the oxidation process. This synergistic action promotes C‐C coupling, resulting in the efficient synthesis of acetic acid.

中文翻译：

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原子分散的Fe-Cu双金属位点协同促进甲烷的羰基化


乙酸是一种重要的工业化学品，传统上通过使用贵金属基均相催化剂对甲醇进行羰基化获得，其生产遇到了设备成本高和可持续性问题带来的挑战。甲烷的直接液相氧化羰基化是一种有前途的替代方案，它利用丰富的天然气资源，并且具有潜在的温和且简单的过程。然而，由于活性位点的缺乏和C1含氧化合物的快速生成，大多数用于该过程的催化剂都存在乙酸收率低的问题，这给后续的羰基化带来了困难并阻碍了其工业可行性。在此，我们报道了一种高效的 0.1Cu/Fe-HZ5-TF 催化剂，其特点是仅锚定在 ZSM-5 通道中的单核 Fe 和 Cu。在优化条件下，该催化剂在 50 °C 下实现了前所未有的乙酸产率 40.5 mmol gcat-1 h-1，超过之前的最大值（12.0 mmol gcat-1h-1）三倍多。综合表征、同位素标记实验和 DFT 计算表明，均质单核 Fe 位点负责甲烷的活化和氧化，而邻近的 Cu 位点在延缓氧化过程中发挥着关键作用。这种协同作用促进 C-C 偶联，从而有效合成乙酸。