Initial Carbon-Carbon Bond Formation during the Early Stages of Methane Dehydroaromatization

作者:Caglayan, M (Caglayan, Mustafa)[ 1 ] ; Paioni, AL (Paioni, Alessandra Lucini)[ 3 ] ; Abou-Hamad, E (Abou-Hamad, Edy)[ 2 ] ; Shterk, G (Shterk, Genrikh)[ 1 ] ; Pustovarenko, A (Pustovarenko, Alexey)[ 1 ] ; Baldus, M (Baldus, Marc)[ 3 ] ; Chowdhury, AD (Chowdhury, Abhishek Dutta)[ 1,4 ] ; Gascon, J (Gascon, Jorge)[ 1 ]

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION

卷: 59

期: 38

页: 16741-16746

DOI: 10.1002/anie.202007283

出版年: SEP 14 2020

在线发表日期: JUL 2020

文献类型:Article

摘要

Methane dehydroaromatization (MDA) is among the most challenging processes in catalysis science owing to the inherent harsh reaction conditions and fast catalyst deactivation. To improve this process, understanding the mechanism of the initial C-C bond formation is essential. However, consensus about the actual reaction mechanism is still to be achieved. In this work, using advanced magic-angle spinning (MAS) solid-state NMR spectroscopy, we study in detail the early stages of the reaction over a well-dispersed Mo/H-ZSM-5 catalyst. Simultaneous detection of acetylene (i.e., presumably the direct C-C bond-forming product from methane), methylidene, allenes, acetal, and surface-formate species, along with the typical olefinic/aromatic species, allow us to conclude the existence of at least two independent C-H activation pathways. Moreover, this study emphasizes the significance of mobility-dependent host-guest chemistry between an inorganic zeolite and its trapped organic species during heterogeneous catalysis.

关键词

作者关键词:bifunctional catalysts; methane dehydroaromatization; reaction mechanisms; solid-state NMR spectroscopy; zeolites

KeyWords Plus:DIMETHYL ETHER; OLEFIN-METATHESIS; METHYL ACETATE; ZEOLITE; AROMATIZATION; MO/HZSM-5; NMR; CATALYST; SURFACE; DEHYDROGENATION

作者信息

通讯作者地址:

King Abdullah University of Science & Technology King Abdullah Univ Sci & Technol KAUST, KAUST Catalysis Ctr KCC, Adv Catalyt Mat, Thuwal 23955, Saudi Arabia.

Wuhan University Wuhan Univ, Inst Adv Studies IAS, Wuhan 430072, Peoples R China.

通讯作者地址: Chowdhury, AD; Gascon, J (通讯作者)

 King Abdullah Univ Sci & Technol KAUST, KAUST Catalysis Ctr KCC, Adv Catalyt Mat, Thuwal 23955, Saudi Arabia.

通讯作者地址: Chowdhury, AD (通讯作者)

 Wuhan Univ, Inst Adv Studies IAS, Wuhan 430072, Peoples R China.

地址:

 [ 1 ]‎ King Abdullah Univ Sci & Technol KAUST, KAUST Catalysis Ctr KCC, Adv Catalyt Mat, Thuwal 23955, Saudi Arabia

 [ 2 ]‎ King Abdullah Univ Sci & Technol, Imaging & Characterizat Dept, Core Labs, Thuwal 23955, Saudi Arabia

 [ 3 ]‎ Univ Utrecht, Bijvoet Ctr Biomol Res, NMR Spect Grp, Padualaan 8, NL-3584 CH Utrecht, Netherlands

 [ 4 ]‎ Wuhan Univ, Inst Adv Studies IAS, Wuhan 430072, Peoples R China

电子邮件地址:abhishek@whu.edu.cn; jorge.gascon@kaust.edu.sa