The direct and selective conversion of syngas into C2+ oxygenates is challenging due to the complex reaction network. Here, we report a robust relay system for the direct synthesis of methyl acetate (MA) from syngas, which combines CuZnAlOx/H‐ZSM‐5 for syngas to dimethyl ether (DME) with modified H‐MOR for DME carbonylation. The dehydration of methanol to DME on H‐ZSM‐5 significantly enhanced the hydrogenation of CO on CuZnAlOx, because of high DME equilibrium yields. Blocking of Brönsted acid sites with basic molecules or selective dealumination of 12‐membered rings in H‐MOR suppressed the zeolite coking. Besides, reaction temperatures above 240°C avoided H2O poisoning of carbonylation sites inside 8‐MR side pockets of H‐MOR, further benefiting the catalytic stability. Eventually, this relay system provided a high MA selectivity of 75% and an acetic acid selectivity of 13% at a CO conversion of 65%, outperforming reported catalysts.

中文翻译：

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通过继电器催化将合成气直接转化为乙酸甲酯：从活性位点的制造到过程控制


由于反应网络复杂，合成气直接选择性地转化为 C2+ 含氧化合物具有挑战性。在这里，我们报道了一种用于从合成气中直接合成乙酸甲酯 （MA） 的稳健中继系统，该系统将用于合成气的 CuZnAlOx/H-ZSM-5 与用于 DME 羰基化的改性 H-MOR 相结合。由于 DME 平衡产率高，甲醇在 H-ZSM-5 上脱水为 DME 显著增强了 CO 在 CuZnAlOx 上的氢化反应。在 H-MOR 中用碱性分子封闭 Brönsted 酸位点或 12 元环的选择性脱离抑制了沸石焦化。此外，高于 240°C 的反应温度避免了 H-MOR 的 8-MR 侧袋内羰基化位点的 H2O 中毒，进一步有利于催化稳定性。最终，该中继系统在 65% 的 CO 转化率下提供了 75% 的高 MA 选择性和 13% 的乙酸选择性，性能优于已报道的催化剂。