The rise and fall of direct mechanisms in methanol-to-olefin catalysis: An overview of theoretical contributions
The rise and fall of direct mechanisms in methanol-to-olefin catalysis: An overview of theoretical contributions
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DOI：
10.1021/ie0613974
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发表时间：
2007-12-19
影响因子：
4.2
通讯作者：
Waroquier, Michel
中科院分区：
文献类型：
--
作者：
Lesthaeghe, David;Van Speybroeck, Veronique;Waroquier, Michel
在过去的30年里，工业界和学术界对酸性沸石上的甲醇制烯烃（MTO）过程进行了大量的研究，对最可能的反应机理产生了许多争议。在过去十年中，计算设备的改进导致了理论贡献的突然增加，当单独考虑时，所有理论似乎都为通常提出的直接机制的部分途径提供了合理的证据。不仅对实验研究提出的反应进行了研究，而且还发现了新的潜在途径。然而，当最近将分散在文献中的所有单个反应结合起来时，理论上得到的速率系数却显示出完全相反的结果，即仅从甲醇产生乙烯的直接机制完全失败。在本文中，我们详细概述了最初支持直接机制提案的理论贡献，但最终以其消亡告终。
Over the past 30 years, the methanol-to-olefin (MTO) process on acidic zeolites has been subject to a vast number of studies from both industrial and academic researchers, leading to numerous controversies regarding the most probable reaction mechanism. Improvement of computational facilities during the past decade led to a sudden boost of theoretical contributions that, when considered individually, all seemed to provide reasonable evidence for partial pathways of the commonly proposed direct mechanisms. Not only the reactions suggested by experimental studies were investigated, but in addition novel potential routes were discovered by theoreticians as well. However, when all of the individual reactions scattered throughout the literature were recently combined, theoretically obtained rate coefficients turned out to show the exact opposite, that is, the complete failure of the direct mechanisms to produce ethylene from methanol only. In this paper, we give a detailed overview of the theoretical contributions that initially supported the direct mechanism proposal, but which finally culminated in its demise.