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氢转移引发的烷烃活化:H-ZSM-5 沸石上丙烷和甲醇的共转化。

Alkane Activation Initiated by Hydride Transfer: Co-conversion of Propane and Methanol over H-ZSM-5 Zeolite.

机构信息

State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou, Gansu 730000 (P. R. China).

Collaborative Innovation Center of Chemical Science and Engineering, Tianjin 300071 (P. R. China).

出版信息

Angew Chem Int Ed Engl. 2015 Jun 15;54(25):7363-6. doi: 10.1002/anie.201501248. Epub 2015 May 8.

Abstract

Co-conversion of alkane with another reactant over zeolite catalysts has emerged as a new approach to the long-standing challenge of alkane transformation. With the aid of solid-state NMR spectroscopy and GC-MS analysis, it was found that the co-conversion of propane and methanol can be readily initiated by hydride transfer at temperatures of ≥449 K over the acidic zeolite H-ZSM-5. The formation of (13)C-labeled methane and singly (13)C-labeled n-butanes in selective labeling experiments provided the first evidence for the initial hydride transfer from propane to surface methoxy intermediates. The results not only provide new insight into carbocation chemistry of solid acids, but also shed light on the low-temperature transformation of alkanes for industrial applications.

摘要

在沸石催化剂上与另一种反应物共转化烷烃已成为烷烃转化这一长期存在的挑战的一种新方法。借助固态 NMR 光谱和 GC-MS 分析,发现丙烯和甲醇在酸性沸石 H-ZSM-5 上,在≥449 K 的温度下,通过氢化物转移可以很容易地引发共转化。在选择性标记实验中,(13)C 标记的甲烷和单(13)C 标记的正丁烷的形成首次提供了从丙烷到表面甲氧基中间体的初始氢化物转移的证据。该结果不仅为固体酸的碳正离子化学提供了新的见解,而且为烷烃的低温转化在工业应用中提供了思路。

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