A Mechanistic Study of Methanol-to-Aromatics Reaction over Ga-Modified ZSM-5 Zeolites: Understanding the Dehydrogenation Process

doi:10.1021/acscatal.8b03076

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	A Mechanistic Study of Methanol-to-Aromatics Reaction over Ga-Modified ZSM-5 Zeolites: Understanding the Dehydrogenation Process
	Deng, Feng 4; Li, Jinlin 1,2; Zhao, Xingling 3,4; Feng, Ningdong 4; Zhang, Yuhua 1,2; Zhao, Yanxi 1,2; Wang, Qiang 4; Wang, Chao 4; Qi, Guodong 4; Xu, Jun 4
刊名	ACS CATALYSIS
	2018-10-01
卷号	8 期号:10 页码:9809-9820
关键词	methanol-to-aromatics dehydrogenation process mechanism metal-modified zeolite solid-state NMR spectroscopy
ISSN号	2155-5435
DOI	10.1021/acscatal.8b03076
英文摘要	The methanol-to-aromatics (MTA) reaction was investigated on Ga-modified ZSM-5 zeolites (Ga/ZSM-5). As revealed by Ga-71 and H-1 solid-state NMR and FT-IR of pyridine adsorption measurements, cationic Ga species are formed as Lewis acid sites by substitution of Bronsted acid sites on H-ZSM-5. Further experimental studies show that C-5- and C-6-cycloalkenes are generated during the MTA reaction, which lead to the formation of cyclic carbocations as precursors to aromatics. Isotope exchange experiments demonstrate that the reactivity of the cyclic carbocations on Ga/ZSM-5 is much higher than that on H-ZSM-5 and they play an intermediate role in the formation of aromatics. In addition to the traditional bimolecular hydrogen transfer (HT) reaction, the dehydrogenation of alkenes with the release of H-2 (DeaH(2) process) was identified to significantly contribute to the formation of aromatics. The transformation of cycloalkenes to aromatics is favored by promotion of the DeaH(2) process and competes with the HT route on Ga/ZSM-5, while these cycloalkenes tend to crack back to alkenes, and the dominating HT route results in lower aromatic selectivity on H-ZSM-5. A DeaH(2)-aromatization route mediated by the cooperation of cationic Ga species and Bronsted acid sites was proposed for the enhanced formation of aromatics on Ga/ZSM-5 zeolite.
资助项目	National Natural Science Foundation of China[21622311] ; National Natural Science Foundation of China[21473245] ; National Natural Science Foundation of China[21603265] ; National Natural Science Foundation of China[21733013] ; key program for frontier science of the Chinese Academy of Sciences[QYZDB-SSW-SLH027]
WOS关键词	STATE NMR-SPECTROSCOPY ; CATALYZED METHYLATION REACTIONS ; BRONSTED/LEWIS ACID SYNERGY ; CHEMICAL-VAPOR-DEPOSITION ; PROPANE AROMATIZATION ; SELECTIVE CONVERSION ; OLEFINS CONVERSION ; HYDROGEN-TRANSFER ; HYDROCARBON-POOL ; HZSM-5 CATALYSTS
WOS研究方向	Chemistry
语种	英语
出版者	AMER CHEMICAL SOC
WOS记录号	WOS:000447224100089
资助机构	National Natural Science Foundation of China ; National Natural Science Foundation of China ; key program for frontier science of the Chinese Academy of Sciences ; key program for frontier science of the Chinese Academy of Sciences ; National Natural Science Foundation of China ; National Natural Science Foundation of China ; key program for frontier science of the Chinese Academy of Sciences ; key program for frontier science of the Chinese Academy of Sciences ; National Natural Science Foundation of China ; National Natural Science Foundation of China ; key program for frontier science of the Chinese Academy of Sciences ; key program for frontier science of the Chinese Academy of Sciences ; National Natural Science Foundation of China ; National Natural Science Foundation of China ; key program for frontier science of the Chinese Academy of Sciences ; key program for frontier science of the Chinese Academy of Sciences
内容类型	期刊论文
源URL	[http://ir.wipm.ac.cn/handle/112942/13329]
专题	武汉物理与数学研究所_磁共振应用研究部
通讯作者	Deng, Feng; Xu, Jun
作者单位	1.South Cent Univ Nationalities, Minist Educ, Wuhan 430074, Peoples R China 2.South Cent Univ Nationalities, Key Lab Catalysis & Mat Sci, State Ethn Affairs Commiss, Wuhan 430074, Peoples R China 3.Univ Chinese Acad Sci, Beijing 100049, Peoples R China 4.Chinese Acad Sci, State Key Lab Magnet Resonance & Atom & Mol Phys, Natl Ctr Magnet Resonance Wuhan, Wuhan Inst Phys & Math,Key Lab Magnet Resonance B, Wuhan 430071, Peoples R China
推荐引用方式 GB/T 7714	Deng, Feng,Li, Jinlin,Zhao, Xingling,et al. A Mechanistic Study of Methanol-to-Aromatics Reaction over Ga-Modified ZSM-5 Zeolites: Understanding the Dehydrogenation Process[J]. ACS CATALYSIS,2018,8(10):9809-9820.
APA	Deng, Feng.,Li, Jinlin.,Zhao, Xingling.,Feng, Ningdong.,Zhang, Yuhua.,...&Gao, Pan.(2018).A Mechanistic Study of Methanol-to-Aromatics Reaction over Ga-Modified ZSM-5 Zeolites: Understanding the Dehydrogenation Process.ACS CATALYSIS,8(10),9809-9820.
MLA	Deng, Feng,et al."A Mechanistic Study of Methanol-to-Aromatics Reaction over Ga-Modified ZSM-5 Zeolites: Understanding the Dehydrogenation Process".ACS CATALYSIS 8.10(2018):9809-9820.