A Spectroscopic Paradox: The Interaction of Methanol with ZSM-5 at Room Temperature

Andrea Zachariou; Alexander P. Hawkins; Russell F. Howe; Nathan Barrow; Jonathan Bradley; Paul Collier; David Lennon; Stewart F. Parker

doi:10.1007/s11244-021-01462-9

A Spectroscopic Paradox: The Interaction of Methanol with ZSM-5 at Room Temperature

Andrea Zachariou
, Alexander P. Hawkins
, Russell F. Howe
, Nathan Barrow
, Jonathan Bradley
, Paul Collier
, David Lennon
, Stewart F. Parker^*

^*Corresponding author for this work

Chemistry

University of Glasgow
Rutherford Appleton Laboratory
Johnson Matthey Plc

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

9 Citations (Scopus)

3 Downloads (Pure)

Abstract

The adsorption of methanol in HZSM-5 at low temperatures has long been regarded as an associative process involving hydrogen bonding to the acidic zeolite hydroxyl groups. Recent studies employing inelastic neutron scattering spectroscopy (INS) have reported that complete dissociation to methoxylate the zeolite occurs at 298 K, and infrared evidence for a partial dissociation at 298 K has also been described. Here we investigate the apparent contradictions between different techniques, using a combination of INS, infrared spectroscopy and solid-state NMR spectroscopy, including isotopic substitution experiments. Different possible explanations are proposed and considered; we conclude that at room temperature methanol is very largely associatively adsorbed, although the presence of some small extent (>1%) of methoxylation cannot be ruled out.

Original language	English
Pages (from-to)	672-684
Number of pages	13
Journal	Topics in Catalysis
Volume	64
Issue number	9-12
Early online date	29 Jul 2021
DOIs	https://doi.org/10.1007/s11244-021-01462-9
Publication status	Published - Aug 2021

Bibliographical note

Funding Information:
Johnson Matthey plc. is thanked for supplying the ZSM-5 zeolite and for financial support through the provision of industrial CASE studentships in partnership with the EPSRC (APH (EP/P510506/1, AZ (EP/N509176/1)). Experiments at the ISIS Neutron and Muon Source were made possible by beam time allocations from the Science and Technologies Facilities Council [–]. The resources and support provided by the UK Catalysis Hub via membership of the UK Catalysis Hub consortium and funded by EPSRC grants EP/R026815/1 and EP/R026939/1 are gratefully acknowledged. This research has been performed with the use of facilities and equipment at the Research Complex at Harwell; the authors are grateful to the Research Complex for this access and support.

Publisher Copyright:
© 2021, The Author(s).

Funding

Johnson Matthey plc. is thanked for supplying the ZSM-5 zeolite and for financial support through the provision of industrial CASE studentships in partnership with the EPSRC (APH (EP/P510506/1, AZ (EP/N509176/1)). Experiments at the ISIS Neutron and Muon Source were made possible by beam time allocations from the Science and Technologies Facilities Council [–]. The resources and support provided by the UK Catalysis Hub via membership of the UK Catalysis Hub consortium and funded by EPSRC grants EP/R026815/1 and EP/R026939/1 are gratefully acknowledged. This research has been performed with the use of facilities and equipment at the Research Complex at Harwell; the authors are grateful to the Research Complex for this access and support. Johnson Matthey plc. is thanked for supplying the ZSM-5 zeolite and for financial support through the provision of industrial CASE studentships in partnership with the EPSRC (APH (EP/P510506/1, AZ (EP/N509176/1)). Experiments at the ISIS Neutron and Muon Source were made possible by beam time allocations from the Science and Technologies Facilities Council [35 ?38]. The resources and support provided by the UK Catalysis Hub via membership of the UK Catalysis Hub consortium and funded by EPSRC grants EP/R026815/1 and EP/R026939/1 are gratefully acknowledged. This research has been performed with the use of facilities and equipment at the Research Complex at Harwell; the authors are grateful to the Research Complex for this access and support.

Keywords

DRIFTS
Hydrogen bonded methanol
HZSM-5
Inelastic neutron scattering (INS)
NMR
Room temperature methoxylation

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Cite this

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title = "A Spectroscopic Paradox: The Interaction of Methanol with ZSM-5 at Room Temperature",

abstract = "The adsorption of methanol in HZSM-5 at low temperatures has long been regarded as an associative process involving hydrogen bonding to the acidic zeolite hydroxyl groups. Recent studies employing inelastic neutron scattering spectroscopy (INS) have reported that complete dissociation to methoxylate the zeolite occurs at 298 K, and infrared evidence for a partial dissociation at 298 K has also been described. Here we investigate the apparent contradictions between different techniques, using a combination of INS, infrared spectroscopy and solid-state NMR spectroscopy, including isotopic substitution experiments. Different possible explanations are proposed and considered; we conclude that at room temperature methanol is very largely associatively adsorbed, although the presence of some small extent (>1\%) of methoxylation cannot be ruled out.",

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note = "Funding Information: Johnson Matthey plc. is thanked for supplying the ZSM-5 zeolite and for financial support through the provision of industrial CASE studentships in partnership with the EPSRC (APH (EP/P510506/1, AZ (EP/N509176/1)). Experiments at the ISIS Neutron and Muon Source were made possible by beam time allocations from the Science and Technologies Facilities Council [{\textendash}]. The resources and support provided by the UK Catalysis Hub via membership of the UK Catalysis Hub consortium and funded by EPSRC grants EP/R026815/1 and EP/R026939/1 are gratefully acknowledged. This research has been performed with the use of facilities and equipment at the Research Complex at Harwell; the authors are grateful to the Research Complex for this access and support. Publisher Copyright: {\textcopyright} 2021, The Author(s).",

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AU - Bradley, Jonathan

AU - Collier, Paul

AU - Lennon, David

AU - Parker, Stewart F.

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N2 - The adsorption of methanol in HZSM-5 at low temperatures has long been regarded as an associative process involving hydrogen bonding to the acidic zeolite hydroxyl groups. Recent studies employing inelastic neutron scattering spectroscopy (INS) have reported that complete dissociation to methoxylate the zeolite occurs at 298 K, and infrared evidence for a partial dissociation at 298 K has also been described. Here we investigate the apparent contradictions between different techniques, using a combination of INS, infrared spectroscopy and solid-state NMR spectroscopy, including isotopic substitution experiments. Different possible explanations are proposed and considered; we conclude that at room temperature methanol is very largely associatively adsorbed, although the presence of some small extent (>1%) of methoxylation cannot be ruled out.

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A Spectroscopic Paradox: The Interaction of Methanol with ZSM-5 at Room Temperature

Abstract

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Keywords

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