Origin of High Selectivity of Dimethyl Ether Carbonylation in the 8-Membered Ring Channel of Mordenite Zeolite
文献类型：期刊论文
| 作者 | Chu, Yueying2; Lo, An-Ya1; Wang, Chao2; Deng, Feng2 |
| 刊名 | JOURNAL OF PHYSICAL CHEMISTRY C
 |
| 出版日期 | 2019-06-27 |
| 卷号 | 123期号:25页码:15503-15512 |
| ISSN号 | 1932-7447 |
| DOI | 10.1021/acs.jpcc.9b01874 |
| 英文摘要 | The mechanisms of dimethyl ether (DME) carbonylation in the 8-membered ring (MR) and the 12-MR channels of H-mordenite (H-MOR) zeolite were separately investigated by quantum-chemical methods to unravel the origin of high selectivity of the methyl acetate product in the 8-MR channel. It is shown that not only the formation of surface methoxy species (SMS) but also its following carbonylation reaction are more energetically feasible in the 8-MR channel. Based on the kinetic analysis of the carbonylation reaction in the two channels, the effective rate constants were determined to reveal the reactivity difference. It was found that at 423 K, the effective rate constant in the 8-MR channel was ca. 13 magnitudes higher than that in the 12-MR channel, revealing the unique selectivity for acetyl intermediate formation in the 8-MR channel. The calculated host-guest interaction energies (E-int) provided evidence that the DME carbonylation reaction exclusively occurring in the 8-MR channel can be ascribed to the strong pore confinement. Among the different components of the E-int, the Pauli repulsive interaction (E-Pauli) is responsible for the SMS formation route, while the electrostatic (E-es) and orbital terms (E-oi) dictate the high selectivity of the carbonylation step in the 8-MR channel. These results suggested that the experimental observation of acetyl intermediate species solely in the 8-MR channel could be mainly ascribed to the difference of the Pauli repulsion, electrostatic interaction, and orbital interaction in the two channels. The theoretical results provide new insights into the DME carbonylation reaction mechanism over H-MOR zeolite. |
| WOS关键词 | METHYL ACETATE ; METHANOL CARBONYLATION ; REACTION-MECHANISM ; CATALYZED CARBONYLATION ; BECKMANN REARRANGEMENT ; ACID SITES ; SPECIFICITY ; FRAMEWORK ; ENTHALPY ; ENTROPY |
| 资助项目 | National Natural Science Foundation of China[21773296] ; National Natural Science Foundation of China[21473246] ; National Natural Science Foundation of China[21603265] ; National Natural Science Foundation of China[21733013] |
| WOS研究方向 | Chemistry ; Science & Technology - Other Topics ; Materials Science |
| 语种 | 英语 |
| WOS记录号 | WOS:000473251300015 |
| 出版者 | AMER CHEMICAL SOC |
| 资助机构 | National Natural Science Foundation of China ; National Natural Science Foundation of China ; National Natural Science Foundation of China ; National Natural Science Foundation of China ; National Natural Science Foundation of China ; National Natural Science Foundation of China ; National Natural Science Foundation of China ; National Natural Science Foundation of China |
| 源URL | [http://ir.wipm.ac.cn/handle/112942/14653]  |
| 专题 | 中国科学院武汉物理与数学研究所 |
| 通讯作者 | Deng, Feng |
| 作者单位 | 1.Natl Chin Yi Univ Technol, Dept Chem & Mat Engn, Taichung 41170, Taiwan 2.Chinese Acad Sci, State Key Lab Magnet Resonance & Atom & Mol Phys, Key Lab Magnet Resonance Biol Syst, Natl Ctr Magnet Resonance Wuhan,Wuhan Inst Phys &, Wuhan 430071, Hubei, Peoples R China |
| 推荐引用方式 GB/T 7714 | Chu, Yueying,Lo, An-Ya,Wang, Chao,et al. Origin of High Selectivity of Dimethyl Ether Carbonylation in the 8-Membered Ring Channel of Mordenite Zeolite[J]. JOURNAL OF PHYSICAL CHEMISTRY C,2019,123(25):15503-15512. |
| APA | Chu, Yueying,Lo, An-Ya,Wang, Chao,&Deng, Feng.(2019).Origin of High Selectivity of Dimethyl Ether Carbonylation in the 8-Membered Ring Channel of Mordenite Zeolite.JOURNAL OF PHYSICAL CHEMISTRY C,123(25),15503-15512. |
| MLA | Chu, Yueying,et al."Origin of High Selectivity of Dimethyl Ether Carbonylation in the 8-Membered Ring Channel of Mordenite Zeolite".JOURNAL OF PHYSICAL CHEMISTRY C 123.25(2019):15503-15512. |
入库方式： OAI收割
来源：武汉物理与数学研究所
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