Charge-separation driven mechanism via acylium ion intermediate migration during catalytic carbonylation in mordenite zeolite.
Charge-separation driven mechanism via acylium ion intermediate migration during catalytic carbonylation in mordenite zeolite.
复制标题
丝光沸石催化羰基化过程中通过酰基离子中间迁移的电荷分离驱动机制
DOI：
10.1038/s41467-022-34708-5
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发表时间：
2022-11-19
影响因子：
16.6
通讯作者：
Zheng, Anmin
中科院分区：
文献类型：
--
作者：
Chen, Wei;Tarach, Karolina A.;Yi, Xianfeng;Liu, Zhiqiang;Tang, Xiaomin;Gora-Marek, Kinga;Zheng, Anmin
通过采用从头算分子动力学模拟、固态NMR光谱和快速扫描傅里叶变换红外光谱数据的二维相关分析，提出了一种通过酰基离子形成乙酸甲酯（MA）的新途径（即，结果表明，在丝光沸石的12元环通道中，该反应路线在动力学和热力学上均优于传统的8元环通道中的反应路线.从整个催化循环的角度来看，这两个反应区的分离，即，在8 MR通道中C-C键偶联和在12 MR通道中MA形成有效地避免了高活性乙酰基物质或乙烯酮的聚集，从而减少了不希望的碳存款产生。不同通道的协同效应似乎解释了丝光沸石中迄今尚未完全解释的高羰基化活性，并且这种范例可以使观察到的其他反应的催化活性合理化。羰基化反应的巨大应用要求对反应机理进行详尽的解释。本文提出了二甲醚羰基化反应中，丝光沸石分子筛上酰基离子中间体生成乙酸甲酯的电荷分离驱动机理。
By employing ab initio molecular dynamic simulations, solid-state NMR spectroscopy, and two-dimensional correlation analysis of rapid scan Fourier transform infrared spectroscopy data, a new pathway is proposed for the formation of methyl acetate (MA) via the acylium ion (i.e.,CH3 − C ≡ O+) in 12-membered ring (MR) channel of mordenite by an integrated reaction/diffusion kinetics model, and this route is kinetically and thermodynamically more favorable than the traditional viewpoint in 8MR channel. From perspective of the complete catalytic cycle, the separation of these two reaction zones, i.e., the C-C bond coupling in 8MR channel and MA formation in 12MR channel, effectively avoids aggregation of highly active acetyl species or ketene, thereby reducing undesired carbon deposit production. The synergistic effect of different channels appears to account for the high carbonylation activity in mordenite that has thus far not been fully explained, and this paradigm may rationalize the observed catalytic activity of other reactions. The tremendous application of carbonylation reaction requires the elaborate explanation to reaction mechanism. Here the authors propose a charge-separation driven mechanism of methyl acetate formation via acylium ion intermediate in mordenite zeolite by an integrated reaction/diffusion kinetics model during the dimethyl ether carbonylation.
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影响因子：
12.9
作者：
Cheng, Zaizhe;Huang, Shouying;Ma, Xinbin
通讯作者：
Ma, Xinbin
影响因子：
16.6
作者：
Cheung, P;Bhan, A;Iglesia, E
通讯作者：
Iglesia, E
影响因子：
3.7
作者：
Goedecker, S;Teter, M;Hutter, J
通讯作者：
Hutter, J
通过原位固态核磁共振波谱深入了解丝光沸石上的二甲醚羰基化反应
影响因子：
3.7
作者：
Li, Bojie;Xu, Jun;Deng, Feng
通讯作者：
Deng, Feng
影响因子：
12.9
作者：
Liu, Rongsheng;Zeng, Shu;Liu, Zhongmin
通讯作者：
Liu, Zhongmin