On the dynamic nature of Mo sites for methane dehydroaromatization

Ina Vollmer; Bart Van Der Linden; Samy Ould-Chikh; Antonio Aguilar-Tapia; Irina Yarulina; Edy Abou-Hamad; Yuri G. Sneider; Alma I. Olivos Suarez; Jean Louis Hazemann; Freek Kapteijn; Jorge Gascon

doi:10.1039/c8sc01263f

On the dynamic nature of Mo sites for methane dehydroaromatization

Ina Vollmer, Bart Van Der Linden, Samy Ould-Chikh, Antonio Aguilar-Tapia, Irina Yarulina, Edy Abou-Hamad, Yuri G. Sneider, Alma I. Olivos Suarez, Jean Louis Hazemann, Freek Kapteijn, Jorge Gascon^*

^*Corresponding author for this work

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

45 Scopus citations

Abstract

The mechanism of methane activation on Mo/HZSM-5 is not yet fully understood, despite the great interest in methane dehydroaromatization (MDA) to replace aromatics production in oil refineries. It is difficult to assess the exact nature of the active site due to fast coking. By pre-carburizing Mo/HZSM-5 with carbon monoxide (CO), the MDA active site formation was isolated from coke formation. With this a clear ¹³C NMR signal solely from the active site and not obscured by coke was obtained, and it revealed two types of likely molecular Mo (oxy-)carbidic species in addition to the β-Mo₂C nanoparticles often mentioned in the literature. Furthermore, separating the active site formation from coking by pre-carburization helped us examine how methane is activated on the catalytic site by carrying out MDA using isotopically labelled methane (¹³CH₄). Carbon originating from the pre-formed carbide was incorporated into the main products of the reaction, ethylene and benzene, demonstrating the dynamic behavior of the (oxy-)carbidic active sites.

Original language	English (US)
Pages (from-to)	4801-4807
Number of pages	7
Journal	Chemical Science
Volume	9
Issue number	21
DOIs	https://doi.org/10.1039/c8sc01263f
State	Published - 2018

Bibliographical note

Funding Information:
We gratefully acknowledge the nancial support from the Sabic-NWO CATC1CHEM CHIPP project. Thanks go to Dr Christoph Dittrich (SABIC), Dr Frank Mostert (SABIC) and Dr Xander Nij-huis (SABIC) as well as Prof. Emiel Hensen (TU Eindhoven) and Nikolay Kosinov (TU Eindhoven) for helpful discussion. We also acknowledge the BM26B DUBBLE beamline and the BM16 FAME-UHD beamline of the European Synchrotron Radiation Facility (ESRF), Grenoble, France for letting us use their facilities. Thanks also go to Maarten Gorseling (TU Del) for performing GC-MS analysis. The FAME-UHD project is nancially supported by the French "grand emprunt" EquipEx (EcoX, ANR-10-EQPX-27-01), the CEA-CNRS CRG consortium and the INSU CNRS institute.

Funding Information:
We gratefully acknowledge the financial support from the Sabic- NWO CATC1CHEM CHIPP project. Thanks go to Dr Christoph Dittrich (SABIC), Dr Frank Mostert (SABIC) and Dr Xander Nijhuis (SABIC) as well as Prof. Emiel Hensen (TU Eindhoven) and Nikolay Kosinov (TU Eindhoven) for helpful discussion. We also acknowledge the BM26B DUBBLE beamline and the BM16 FAME-UHD beamline of the European Synchrotron Radiation Facility (ESRF), Grenoble, France for letting us use their facilities. Thanks also go to Maarten Gorseling (TU Delft) for performing GC-MS analysis. The FAME-UHD project is financially supported by the French "grand emprunt" EquipEx (EcoX, ANR- 10-EQPX-27-01), the CEA-CNRS CRG consortium and the INSU CNRS institute.

Publisher Copyright:
© 2018 The Royal Society of Chemistry.

ASJC Scopus subject areas

Chemistry(all)

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10.1039/c8sc01263f

Cite this

@article{b6bb668c423749939f0e3b3d3b88b1fb,

title = "On the dynamic nature of Mo sites for methane dehydroaromatization",

abstract = "The mechanism of methane activation on Mo/HZSM-5 is not yet fully understood, despite the great interest in methane dehydroaromatization (MDA) to replace aromatics production in oil refineries. It is difficult to assess the exact nature of the active site due to fast coking. By pre-carburizing Mo/HZSM-5 with carbon monoxide (CO), the MDA active site formation was isolated from coke formation. With this a clear 13C NMR signal solely from the active site and not obscured by coke was obtained, and it revealed two types of likely molecular Mo (oxy-)carbidic species in addition to the β-Mo2C nanoparticles often mentioned in the literature. Furthermore, separating the active site formation from coking by pre-carburization helped us examine how methane is activated on the catalytic site by carrying out MDA using isotopically labelled methane (13CH4). Carbon originating from the pre-formed carbide was incorporated into the main products of the reaction, ethylene and benzene, demonstrating the dynamic behavior of the (oxy-)carbidic active sites.",

author = "Ina Vollmer and {Van Der Linden}, Bart and Samy Ould-Chikh and Antonio Aguilar-Tapia and Irina Yarulina and Edy Abou-Hamad and Sneider, {Yuri G.} and {Olivos Suarez}, {Alma I.} and Hazemann, {Jean Louis} and Freek Kapteijn and Jorge Gascon",

note = "Funding Information: We gratefully acknowledge the nancial support from the Sabic-NWO CATC1CHEM CHIPP project. Thanks go to Dr Christoph Dittrich (SABIC), Dr Frank Mostert (SABIC) and Dr Xander Nij-huis (SABIC) as well as Prof. Emiel Hensen (TU Eindhoven) and Nikolay Kosinov (TU Eindhoven) for helpful discussion. We also acknowledge the BM26B DUBBLE beamline and the BM16 FAME-UHD beamline of the European Synchrotron Radiation Facility (ESRF), Grenoble, France for letting us use their facilities. Thanks also go to Maarten Gorseling (TU Del) for performing GC-MS analysis. The FAME-UHD project is nancially supported by the French {"}grand emprunt{"} EquipEx (EcoX, ANR-10-EQPX-27-01), the CEA-CNRS CRG consortium and the INSU CNRS institute. Funding Information: We gratefully acknowledge the financial support from the Sabic- NWO CATC1CHEM CHIPP project. Thanks go to Dr Christoph Dittrich (SABIC), Dr Frank Mostert (SABIC) and Dr Xander Nijhuis (SABIC) as well as Prof. Emiel Hensen (TU Eindhoven) and Nikolay Kosinov (TU Eindhoven) for helpful discussion. We also acknowledge the BM26B DUBBLE beamline and the BM16 FAME-UHD beamline of the European Synchrotron Radiation Facility (ESRF), Grenoble, France for letting us use their facilities. Thanks also go to Maarten Gorseling (TU Delft) for performing GC-MS analysis. The FAME-UHD project is financially supported by the French {"}grand emprunt{"} EquipEx (EcoX, ANR- 10-EQPX-27-01), the CEA-CNRS CRG consortium and the INSU CNRS institute. Publisher Copyright: {\textcopyright} 2018 The Royal Society of Chemistry.",

year = "2018",

doi = "10.1039/c8sc01263f",

language = "English (US)",

volume = "9",

pages = "4801--4807",

journal = "Chemical Science",

issn = "2041-6520",

publisher = "Royal Society of Chemistry",

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T1 - On the dynamic nature of Mo sites for methane dehydroaromatization

AU - Vollmer, Ina

AU - Van Der Linden, Bart

AU - Ould-Chikh, Samy

AU - Aguilar-Tapia, Antonio

AU - Yarulina, Irina

AU - Abou-Hamad, Edy

AU - Sneider, Yuri G.

AU - Olivos Suarez, Alma I.

AU - Hazemann, Jean Louis

AU - Kapteijn, Freek

AU - Gascon, Jorge

N1 - Funding Information: We gratefully acknowledge the nancial support from the Sabic-NWO CATC1CHEM CHIPP project. Thanks go to Dr Christoph Dittrich (SABIC), Dr Frank Mostert (SABIC) and Dr Xander Nij-huis (SABIC) as well as Prof. Emiel Hensen (TU Eindhoven) and Nikolay Kosinov (TU Eindhoven) for helpful discussion. We also acknowledge the BM26B DUBBLE beamline and the BM16 FAME-UHD beamline of the European Synchrotron Radiation Facility (ESRF), Grenoble, France for letting us use their facilities. Thanks also go to Maarten Gorseling (TU Del) for performing GC-MS analysis. The FAME-UHD project is nancially supported by the French "grand emprunt" EquipEx (EcoX, ANR-10-EQPX-27-01), the CEA-CNRS CRG consortium and the INSU CNRS institute. Funding Information: We gratefully acknowledge the financial support from the Sabic- NWO CATC1CHEM CHIPP project. Thanks go to Dr Christoph Dittrich (SABIC), Dr Frank Mostert (SABIC) and Dr Xander Nijhuis (SABIC) as well as Prof. Emiel Hensen (TU Eindhoven) and Nikolay Kosinov (TU Eindhoven) for helpful discussion. We also acknowledge the BM26B DUBBLE beamline and the BM16 FAME-UHD beamline of the European Synchrotron Radiation Facility (ESRF), Grenoble, France for letting us use their facilities. Thanks also go to Maarten Gorseling (TU Delft) for performing GC-MS analysis. The FAME-UHD project is financially supported by the French "grand emprunt" EquipEx (EcoX, ANR- 10-EQPX-27-01), the CEA-CNRS CRG consortium and the INSU CNRS institute. Publisher Copyright: © 2018 The Royal Society of Chemistry.

PY - 2018

Y1 - 2018

N2 - The mechanism of methane activation on Mo/HZSM-5 is not yet fully understood, despite the great interest in methane dehydroaromatization (MDA) to replace aromatics production in oil refineries. It is difficult to assess the exact nature of the active site due to fast coking. By pre-carburizing Mo/HZSM-5 with carbon monoxide (CO), the MDA active site formation was isolated from coke formation. With this a clear 13C NMR signal solely from the active site and not obscured by coke was obtained, and it revealed two types of likely molecular Mo (oxy-)carbidic species in addition to the β-Mo2C nanoparticles often mentioned in the literature. Furthermore, separating the active site formation from coking by pre-carburization helped us examine how methane is activated on the catalytic site by carrying out MDA using isotopically labelled methane (13CH4). Carbon originating from the pre-formed carbide was incorporated into the main products of the reaction, ethylene and benzene, demonstrating the dynamic behavior of the (oxy-)carbidic active sites.

AB - The mechanism of methane activation on Mo/HZSM-5 is not yet fully understood, despite the great interest in methane dehydroaromatization (MDA) to replace aromatics production in oil refineries. It is difficult to assess the exact nature of the active site due to fast coking. By pre-carburizing Mo/HZSM-5 with carbon monoxide (CO), the MDA active site formation was isolated from coke formation. With this a clear 13C NMR signal solely from the active site and not obscured by coke was obtained, and it revealed two types of likely molecular Mo (oxy-)carbidic species in addition to the β-Mo2C nanoparticles often mentioned in the literature. Furthermore, separating the active site formation from coking by pre-carburization helped us examine how methane is activated on the catalytic site by carrying out MDA using isotopically labelled methane (13CH4). Carbon originating from the pre-formed carbide was incorporated into the main products of the reaction, ethylene and benzene, demonstrating the dynamic behavior of the (oxy-)carbidic active sites.

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U2 - 10.1039/c8sc01263f

DO - 10.1039/c8sc01263f

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AN - SCOPUS:85047959919

SN - 2041-6520

VL - 9

SP - 4801

EP - 4807

JO - Chemical Science

JF - Chemical Science

IS - 21

ER -

On the dynamic nature of Mo sites for methane dehydroaromatization

Abstract

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