铜(I)丝光沸石上短链烷烃低温非氧化脱氢的化学环反应

IF 15.6 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY
Mikalai A. Artsiusheuski, Jiawei Guo, Ambarish R. Kulkarni*, Jeroen A. van Bokhoven* and Vitaly L. Sushkevich*, 
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引用次数: 0

摘要

本文报道了以含铜丝光沸石为活性物质,通过化学环法对乙烷和丙烷进行选择性低温非氧化脱氢制备乙烯和丙烯。结合Cu k边x射线吸收光谱、原位红外光谱(FTIR)、H/D动力学同位素效应测量和密度泛函数理论计算,我们发现脱氢反应的活性位点是沸石骨架上的铜(I)阳离子,限速步骤是激活烷烃的第一个C-H键。气相烷烃与铜(I)阳离子位发生化学计量反应,形成稳定的铜(I)-烯烃π配合物和气态氢。在573k下,铜(I)位与烯烃完全饱和,选择性接近100%。烯烃与铜(I)位点的强结合促进了脱氢反应,使烯烃的产率比气相热力学极限高100倍以上。铜(I)-烯烃配合物可以在接近环境温度下与水接触,在单独的步骤中分解,将烯烃释放到气相中,并且材料可以再生而不会有可检测到的活性损失。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

Low-Temperature Nonoxidative Dehydrogenation of Short-Chain Alkanes over Copper(I) Mordenite via Chemical Looping

Low-Temperature Nonoxidative Dehydrogenation of Short-Chain Alkanes over Copper(I) Mordenite via Chemical Looping

We report selective low-temperature non-oxidative dehydrogenation of ethane and propane to ethylene and propylene via chemical looping using copper(I)-containing mordenite as active material. Combining Cu K-edge X-ray absorption spectroscopy, in situ infrared spectroscopy (FTIR), H/D kinetic isotope effect measurements, and density functional theory calculations, we show that the active sites for the dehydrogenation reaction are copper(I) cations hosted in zeolite framework, and the rate-limiting step is activation of the first C–H bond of alkane. The stoichiometric reaction between the gas-phase alkane and copper(I) cationic site results in the formation of a stable copper(I)-alkene π-complex and gaseous hydrogen. Complete saturation of copper(I) sites with alkenes can be attained at 573 K with a selectivity close to 100%. The strong binding of alkenes to copper(I) sites promotes the dehydrogenation reaction, enabling the yield of alkene more than 100 times greater than the gas-phase thermodynamic limit. Copper(I)-alkene complexes can be decomposed in a separate step by contact with water at near-ambient temperature, releasing alkenes into the gas phase, and the material can be regenerated without detectable loss of activity.

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来源期刊
CiteScore
24.40
自引率
6.00%
发文量
2398
审稿时长
1.6 months
期刊介绍: The flagship journal of the American Chemical Society, known as the Journal of the American Chemical Society (JACS), has been a prestigious publication since its establishment in 1879. It holds a preeminent position in the field of chemistry and related interdisciplinary sciences. JACS is committed to disseminating cutting-edge research papers, covering a wide range of topics, and encompasses approximately 19,000 pages of Articles, Communications, and Perspectives annually. With a weekly publication frequency, JACS plays a vital role in advancing the field of chemistry by providing essential research.
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