Fast detection and structural identification of carbocations on zeolites by dynamic nuclear polarization enhanced solid-state NMR

doi:10.1039/c8sc03848a

	Fast detection and structural identification of carbocations on zeolites by dynamic nuclear polarization enhanced solid-state NMR
	Xiao, Dong 1,2,3; Xu, Shutao 4; Brownbill, Nick J.3; Paul, Subhradip 5; Chen, Li-Hua 6; Pawsey, Shane 7; Aussenac, Fabien 8; Su, Bao-Lian 6,9; Han, Xiuwen 1; Bao, Xinhe 1
刊名	CHEMICAL SCIENCE
	2018-11-21
卷号	9 期号:43 页码:11
ISSN号	2041-6520
DOI	10.1039/c8sc03848a
通讯作者	Blanc, Frederic(frederic.blanc@liverpool.ac.uk)
英文摘要	Acidic zeolites are porous aluminosilicates used in a wide range of industrial processes such as adsorption and catalysis. The formation of carbocation intermediates plays a key role in reactivity, selectivity and deactivation in heterogeneous catalytic processes. However, the observation and determination of carbocations remain a significant challenge in heterogeneous catalysis due to the lack of selective techniques of sufficient sensitivity to detect their low concentrations. Here, we combine C-13 isotopic enrichment and efficient dynamic nuclear polarization magic angle spinning nuclear magnetic resonance spectroscopy to detect carbocations in zeolites. We use two dimensional C-13-C-13 through-bond correlations to establish their structures and Si-29-C-13 through-space experiments to quantitatively probe the interaction between multiple surface sites of the zeolites and the confined hydrocarbon pool species. We show that a range of various membered ring carbocations are intermediates in the methanol to hydrocarbons reaction catalysed by different microstructural -zeolites and highlight that different reaction routes for the formation of both targeted hydrocarbon products and coke exist. These species have strong van der Waals interaction with the zeolite framework demonstrating that their accumulation in the channels of the zeolites leads to deactivation. These results enable understanding of deactivation pathways and open up opportunities for the design of catalysts with improved performances.
资助项目	BP[75139] ; National Natural Science Foundation of China[91545104] ; National Natural Science Foundation of China[21473182] ; Youth Innovation Promotion Association of the Chinese Academy of Sciences[2014165] ; Engineering and Physical Science Research Council (EPSRC)[EP/M00869X/1] ; Engineering and Physical Science Research Council (EPSRC)[EP/P511353/1] ; University of Nottingham Advanced Molecular Materials RPA ; University of Liverpool[75139] ; Dalian Institute of Chemical Physics[75139] ; EPSRC[EP/L022524/1]
WOS关键词	IN-SITU NMR ; DOUBLE-RESONANCE NMR ; TO-OLEFIN CATALYSIS ; SN-BETA ZEOLITE ; CARBENIUM IONS ; REACTION-MECHANISM ; HEPTAMETHYLBENZENIUM CATION ; H-BETA ; HETEROGENEOUS CATALYSIS ; HYDROCARBONS REACTION
WOS研究方向	Chemistry
语种	英语
出版者	ROYAL SOC CHEMISTRY
WOS记录号	WOS:000449701000003
资助机构	BP ; BP ; National Natural Science Foundation of China ; National Natural Science Foundation of China ; Youth Innovation Promotion Association of the Chinese Academy of Sciences ; Youth Innovation Promotion Association of the Chinese Academy of Sciences ; Engineering and Physical Science Research Council (EPSRC) ; Engineering and Physical Science Research Council (EPSRC) ; University of Nottingham Advanced Molecular Materials RPA ; University of Nottingham Advanced Molecular Materials RPA ; University of Liverpool ; University of Liverpool ; Dalian Institute of Chemical Physics ; Dalian Institute of Chemical Physics ; EPSRC ; EPSRC ; BP ; BP ; National Natural Science Foundation of China ; National Natural Science Foundation of China ; Youth Innovation Promotion Association of the Chinese Academy of Sciences ; Youth Innovation Promotion Association of the Chinese Academy of Sciences ; Engineering and Physical Science Research Council (EPSRC) ; Engineering and Physical Science Research Council (EPSRC) ; University of Nottingham Advanced Molecular Materials RPA ; University of Nottingham Advanced Molecular Materials RPA ; University of Liverpool ; University of Liverpool ; Dalian Institute of Chemical Physics ; Dalian Institute of Chemical Physics ; EPSRC ; EPSRC ; BP ; BP ; National Natural Science Foundation of China ; National Natural Science Foundation of China ; Youth Innovation Promotion Association of the Chinese Academy of Sciences ; Youth Innovation Promotion Association of the Chinese Academy of Sciences ; Engineering and Physical Science Research Council (EPSRC) ; Engineering and Physical Science Research Council (EPSRC) ; University of Nottingham Advanced Molecular Materials RPA ; University of Nottingham Advanced Molecular Materials RPA ; University of Liverpool ; University of Liverpool ; Dalian Institute of Chemical Physics ; Dalian Institute of Chemical Physics ; EPSRC ; EPSRC ; BP ; BP ; National Natural Science Foundation of China ; National Natural Science Foundation of China ; Youth Innovation Promotion Association of the Chinese Academy of Sciences ; Youth Innovation Promotion Association of the Chinese Academy of Sciences ; Engineering and Physical Science Research Council (EPSRC) ; Engineering and Physical Science Research Council (EPSRC) ; University of Nottingham Advanced Molecular Materials RPA ; University of Nottingham Advanced Molecular Materials RPA ; University of Liverpool ; University of Liverpool ; Dalian Institute of Chemical Physics ; Dalian Institute of Chemical Physics ; EPSRC ; EPSRC
内容类型	期刊论文
源URL	[http://cas-ir.dicp.ac.cn/handle/321008/166682]
专题	大连化学物理研究所_中国科学院大连化学物理研究所
通讯作者	Blanc, Frederic
作者单位	1.Chinese Acad Sci, Dalian Inst Chem Phys, State Key Lab Catalysis, 457 Zhongshan Rd, Dalian 116023, Peoples R China 2.Univ Chinese Acad Sci, Beijing 100049, Peoples R China 3.Univ Liverpool, Dept Chem, Crown St, Liverpool L69 7ZD, Merseyside, England 4.Chinese Acad Sci, Dalian Inst Chem Phys, Natl Engn Lab Methanol Olefins, Dalian Natl Lab Clean Energy, Dalian 116023, Peoples R China 5.Univ Nottingham, Sir Peter Mansfield Imaging Ctr, DNP MAS NMR Facil, Nottingham NG7 2RD, England 6.Wuhan Univ Technol, State Key Lab Adv Technol Mat Synth & Proc, 122 Luoshi Rd, Wuhan 430070, Hubei, Peoples R China 7.Bruker BioSpin Corp, 15 Fortune Dr, Billerica, MA 01821 USA 8.Bruker BioSpin, 34 Rue Ind BP 10002, F-67166 Wissembourg, France 9.Univ Namur, CMI, Lab Inorgan Mat Chem, 61 Rue Bruxelles, B-5000 Namur, Belgium 10.Univ Liverpool, Stephenson Inst Renewable Energy, Crown St, Liverpool L69 7ZD, Merseyside, England
推荐引用方式 GB/T 7714	Xiao, Dong,Xu, Shutao,Brownbill, Nick J.,et al. Fast detection and structural identification of carbocations on zeolites by dynamic nuclear polarization enhanced solid-state NMR[J]. CHEMICAL SCIENCE,2018,9(43):11.
APA	Xiao, Dong.,Xu, Shutao.,Brownbill, Nick J..,Paul, Subhradip.,Chen, Li-Hua.,...&Blanc, Frederic.(2018).Fast detection and structural identification of carbocations on zeolites by dynamic nuclear polarization enhanced solid-state NMR.CHEMICAL SCIENCE,9(43),11.
MLA	Xiao, Dong,et al."Fast detection and structural identification of carbocations on zeolites by dynamic nuclear polarization enhanced solid-state NMR".CHEMICAL SCIENCE 9.43(2018):11.