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

Mustafa Çağlayan; Alessandra Lucini Paioni; Edy Abou-Hamad; Genrikh Shterk; Alexey Pustovarenko; Marc Baldus; Abhishek Dutta Chowdhury; Jorge Gascon

doi:10.1002/anie.202007283

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

Mustafa Çağlayan, Alessandra Lucini Paioni, Edy Abou-Hamad, Genrikh Shterk, Alexey Pustovarenko, Marc Baldus, Abhishek Dutta Chowdhury^*, Jorge Gascon^*

^*Corresponding author for this work

King Abdullah University of Science and Technology

Research output: Contribution to journal › Article › Academic › peer-review

Abstract

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.

Original language	English
Pages (from-to)	16741-16746
Number of pages	6
Journal	Angewandte Chemie - International Edition
Volume	59
Issue number	38
DOIs	https://doi.org/10.1002/anie.202007283
Publication status	Published - 14 Sept 2020

Funding

Funding for this work was provided by King Abdullah University of Science and Technology (KAUST). ADC also thanks the starting grant support from IAS, Wuhan University. ALP was supported by a TOP-PUNT grant (no. 718.015.001) to M.B. from Netherlands Organization of Scientific Research (NWO).

Keywords

bifunctional catalysts
methane dehydroaromatization
reaction mechanisms
solid-state NMR spectroscopy
zeolites

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10.1002/anie.202007283

anie.202007283Final published version, 2.72 MBLicence: Taverne

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title = "Initial Carbon−Carbon Bond Formation during the Early Stages of Methane Dehydroaromatization",

abstract = "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.",

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AU - Çağlayan, Mustafa

AU - Lucini Paioni, Alessandra

AU - Abou-Hamad, Edy

AU - Shterk, Genrikh

AU - Pustovarenko, Alexey

AU - Baldus, Marc

AU - Chowdhury, Abhishek Dutta

AU - Gascon, Jorge

PY - 2020/9/14

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N2 - 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.

AB - 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.

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KW - solid-state NMR spectroscopy

KW - zeolites

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

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