Ca Cations Impact the Local Environment inside HZSM-5 Pores during the Methanol-to-Hydrocarbons Reaction

Anna Liutkova, Hao Zhang, Jérôme F.M. Simons, Brahim Mezari, Marta Mirolo, Gustavo A. Garcia, Emiel J.M. Hensen (Corresponding author), Nikolay Kosinov (Corresponding author)

Research output: Contribution to journalArticleAcademicpeer-review

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The methanol-to-hydrocarbons (MTH) process is an industrially relevant method to produce valuable light olefins such as propylene. One of the ways to enhance propylene selectivity is to modify zeolite catalysts with alkaline earth cations. The underlying mechanistic aspects of this type of promotion are not well understood. Here, we study the interaction of Ca2+ with reaction intermediates and products formed during the MTH reaction. Using transient kinetic and spectroscopic tools, we find strong indications that the selectivity differences between Ca/ZSM-5 and HZSM-5 are related to the different local environment inside the pores due to the presence of Ca2+. In particular, Ca/ZSM-5 strongly retains water, hydrocarbons, and oxygenates, which occupy as much as 10% of the micropores during the ongoing MTH reaction. This change in the effective pore geometry affects the formation of hydrocarbon pool components and in this way directs the MTH reaction toward the olefin cycle.
Original languageEnglish
Pages (from-to)3471-3484
Number of pages14
JournalACS Catalysis
Issue number6
Publication statusPublished - 17 Mar 2023


FundersFunder number
Netherlands Center for Multiscale Catalytic Energy Conversion
European Union 's Horizon 2020 - Research and Innovation Framework Programme
Marie Skłodowska‐Curie801359
European Synchrotron Radiation FacilityCH6231, CH6391
Ministerie van Onderwijs, Cultuur en Wetenschap
Nederlandse Organisatie voor Wetenschappelijk Onderzoek


    • alcohols
    • Aromatic compounds
    • catalysts
    • hydrocarbons
    • zeolites
    • methanol-to-hydrocarbons
    • zeolite, Ca/ZSM-5
    • confinement
    • hydrocarbon pool
    • step-response kinetic experiments
    • operando spectroscopy


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