St Andrews Research Repository

St Andrews University Home
View Item 
  •   St Andrews Research Repository
  • University of St Andrews Research
  • University of St Andrews Research
  • University of St Andrews Research
  • View Item
  •   St Andrews Research Repository
  • University of St Andrews Research
  • University of St Andrews Research
  • University of St Andrews Research
  • View Item
  •   St Andrews Research Repository
  • University of St Andrews Research
  • University of St Andrews Research
  • University of St Andrews Research
  • View Item
  • Login
JavaScript is disabled for your browser. Some features of this site may not work without it.

Carbene-like reactivity of methoxy groups in a single crystal SAPO-34 MTO catalyst

Thumbnail
View/Open
SAPO_34_SI_accepted.pdf (1.585Mb)
SAPO_34_manuscript_accepted.pdf (2.243Mb)
Date
21/02/2022
Author
Minova, Ivalina
Buehl, Michael
Matam, Santhosh
Catlow, C. Richard A.
Frogley, Mark
Cinque, Gianfelice
Wright, Paul A.
Howe, Russell
Funder
EPSRC
Grant ID
EP/L016419/1
Keywords
QD Chemistry
DAS
MCP
Metadata
Show full item record
Altmetrics Handle Statistics
Altmetrics DOI Statistics
Abstract
Synchrotron FTIR microspectroscopy coupled with mass spectrometric analysis of desorbed products has been used to investigate the initial stages of the methanol to olefins (MTO) reaction in single crystals of SAPO-34. Surface methoxy groups (SMS) are key to initial dimethylether (DME) and subsequent carbon–carbon bond formation. Deprotonation of SMS is the critical first step in direct olefin formation at low temperatures and DME is not involved in the carbon–carbon forming step. Experiments with CD3OH confirm the deprotonation step and show an inverse kinetic isotope effect consistent with irreversible deprotonation. The subsequent formation of alkoxide species, which are the precursors of the olefinic hydrocarbon pool present in working MTO catalysts, is initiated via insertion of surface carbene-like species into adjacent SMS. The observed induction period for this process is determined by the limited mobility of SMS and/or carbene species. Olefins formed from cracking of the alkoxide species then transmit carbon–carbon bond formation through the SAPO-34 by rapid diffusion and reaction with further SMS. Acetyl species seen with methanol at higher temperatures support the insertion of CO into SMS suggested in the literature, but these species do not play a role in direct olefin formation.
Citation
Minova , I , Buehl , M , Matam , S , Catlow , C R A , Frogley , M , Cinque , G , Wright , P A & Howe , R 2022 , ' Carbene-like reactivity of methoxy groups in a single crystal SAPO-34 MTO catalyst ' , Catalysis Science & Technology . https://doi.org/10.1039/D1CY02361F
Publication
Catalysis Science & Technology
Status
Peer reviewed
DOI
https://doi.org/10.1039/D1CY02361F
ISSN
2044-4753
Type
Journal article
Rights
Copyright © 2022 The Author(s). This work has been made available online in accordance with publisher policies or with permission. Permission for further reuse of this content should be sought from the publisher or the rights holder. This is the author created accepted manuscript following peer review and may differ slightly from the final published version. The final published version of this work is available at https://doi.org/10.1039/D1CY02361F
Description
IBM and PAW would like to thank the EPSRC and CRITICAT Centre for Doctoral Training for Financial Support (PhD studentship to IBM EP/I017008/1), and supplementary equipment grant EP/L016419/1]. The UK Catalysis Hub is thanked for resources and support provided via membership of the UK Catalysis Hub Consortium and funded by EPSRC (grants EP/I038748/1, EP/I019693/1, EP/K014706/1, EP/K014668/1, EP/K014854/1, EP/K014714/1 and EP/M013219/1).
Collections
  • University of St Andrews Research
URI
http://hdl.handle.net/10023/27018

Items in the St Andrews Research Repository are protected by copyright, with all rights reserved, unless otherwise indicated.

Advanced Search

Browse

All of RepositoryCommunities & CollectionsBy Issue DateNamesTitlesSubjectsClassificationTypeFunderThis CollectionBy Issue DateNamesTitlesSubjectsClassificationTypeFunder

My Account

Login

Open Access

To find out how you can benefit from open access to research, see our library web pages and Open Access blog. For open access help contact: openaccess@st-andrews.ac.uk.

Accessibility

Read our Accessibility statement.

How to submit research papers

The full text of research papers can be submitted to the repository via Pure, the University's research information system. For help see our guide: How to deposit in Pure.

Electronic thesis deposit

Help with deposit.

Repository help

For repository help contact: Digital-Repository@st-andrews.ac.uk.

Give Feedback

Cookie policy

This site may use cookies. Please see Terms and Conditions.

Usage statistics

COUNTER-compliant statistics on downloads from the repository are available from the IRUS-UK Service. Contact us for information.

© University of St Andrews Library

University of St Andrews is a charity registered in Scotland, No SC013532.

  • Facebook
  • Twitter