In situ generation by cyclization of an organic structure directing agent for the synthesis of high silica zeolite ERS-7

Magdalena M. Lozinska; Ruxandra G. Chitac; Elliott L. Bruce; Malavika Manoj; Yuanyuan Du; Daniel M. Dawson; Sharon E. Ashbrook; Paul A. Cox; Paul A. Wright

doi:10.1002/chem.202500327

In situ generation by cyclization of an organic structure directing agent for the synthesis of high silica zeolite ERS-7

Magdalena M. Lozinska, Ruxandra G. Chitac, Elliott L. Bruce, Malavika Manoj, Yuanyuan Du, Daniel M. Dawson, Sharon E. Ashbrook, Paul A. Cox, Paul A. Wright^*

^*Corresponding author for this work

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

Abstract

Zeolites with high framework Si/Al ratios are of interest for industrial applications due to their hydrothermal stability. They are usually synthesized in the presence of pre-prepared organic structure directing agents (OSDAs). The high silica ERS-7 zeolite (topology type ESV) can be crystallized using N,N-dimethylpyrrolidinium (dmpyrr) that is formed in situ via cyclization of N,N,N’,N’-tetramethyl-1,4-diaminobutane (tmdab) when a cationic polymer is also present. The in situ generation of dmpyrr is demonstrated by solid-state ¹³C NMR spectroscopy and supported by both chemical analyses and comparative syntheses using pre-prepared dmpyrr. The cationic polymer inhibits the crystallization of mordenite, which is otherwise observed to be the favored product. The ERS-7 prepared via in situ dmpyrr synthesis (Si/Al = 14) is characterized by PXRD and solid-state NMR spectroscopy. The CO₂ adsorption seen for the H- and Na-forms indicates interactions with accessible Na⁺ cations. The synthetic studies indicate the potential for in situ generation of OSDAs to reduce the need for extended OSDA syntheses.

Original language	English
Article number	e202500327
Number of pages	11
Journal	Chemistry - A European Journal
Volume	Early View
Early online date	7 May 2025
DOIs	https://doi.org/10.1002/chem.202500327
Publication status	E-pub ahead of print - 7 May 2025

Keywords

Cationic polymer
ESV topology type
In situ OSDA formation
Zeolite synthesis

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Lozinska_2025_CaEJ_In-situ-generation-cyclization-high-silica-zeolite-ERS-7_CC
© 2025 The Author(s). This is an open access article under the terms of the Creative Commons Attribution License (https://creativecommons.org/licenses/by/4.0/), which permits use, distribution and reproduction in any medium, provided the original work is properly cited.
Final published version, 3.01 MBLicence: CC BY

Light Element Analysis Facility (LEAF): Light Element Analysis Facility (LEAF)
Irvine, J. T. S. (PI), Baker, R. (CoI) & Miller, D. N. (CoI)
EPSRC
5/04/20 → 4/04/23
Project: Standard
Designed Synthesis of Zeolites for Envir: Designed Synthesis of Zeolites for Environmental and Biorenewables Catalysis
Wright, P. A. (PI) & Ashbrook, S. E. (CoI)
EPSRC
1/02/19 → 30/11/22
Project: Standard
Electon Microscopy: Electon Microscopy for the characterisation and manipulation of advanced function materials and their interfaces at the nanoscale
Irvine, J. T. S. (PI), Baker, R. (CoI) & Zhou, W. (CoI)
EPSRC
1/04/18 → 2/09/20
Project: Standard

In Situ Generation by Cyclisation of an Organic Structure Directing Agent for the Synthesis of High Silica Zeolite ERS-7 (dataset)
Lozinska, M. M. (Creator), Chitac, R.-G. (Creator), Bruce, E. L. (Creator), Du, Y. (Creator), Manoj, M. (Creator), Dawson, D. M. (Creator), Ashbrook, S. E. (Creator), Cox, P. A. (Creator) & Wright, P. A. (Creator), University of St Andrews, 2 May 2025
DOI: 10.17630/46025e62-37ec-4907-8e67-1f77543eab7d
Dataset

File

Cite this

Lozinska, M. M., Chitac, R. G., Bruce, E. L., Manoj, M., Du, Y., Dawson, D. M., Ashbrook, S. E., Cox, P. A., & Wright, P. A. (2025). In situ generation by cyclization of an organic structure directing agent for the synthesis of high silica zeolite ERS-7. Chemistry - A European Journal, Early View, Article e202500327. Advance online publication. https://doi.org/10.1002/chem.202500327

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title = "In situ generation by cyclization of an organic structure directing agent for the synthesis of high silica zeolite ERS-7",

abstract = "Zeolites with high framework Si/Al ratios are of interest for industrial applications due to their hydrothermal stability. They are usually synthesized in the presence of pre-prepared organic structure directing agents (OSDAs). The high silica ERS-7 zeolite (topology type ESV) can be crystallized using N,N-dimethylpyrrolidinium (dmpyrr) that is formed in situ via cyclization of N,N,N{\textquoteright},N{\textquoteright}-tetramethyl-1,4-diaminobutane (tmdab) when a cationic polymer is also present. The in situ generation of dmpyrr is demonstrated by solid-state 13C NMR spectroscopy and supported by both chemical analyses and comparative syntheses using pre-prepared dmpyrr. The cationic polymer inhibits the crystallization of mordenite, which is otherwise observed to be the favored product. The ERS-7 prepared via in situ dmpyrr synthesis (Si/Al = 14) is characterized by PXRD and solid-state NMR spectroscopy. The CO2 adsorption seen for the H- and Na-forms indicates interactions with accessible Na+ cations. The synthetic studies indicate the potential for in situ generation of OSDAs to reduce the need for extended OSDA syntheses.",

keywords = "Cationic polymer, ESV topology type, In situ OSDA formation, Zeolite synthesis",

author = "Lozinska, {Magdalena M.} and Chitac, {Ruxandra G.} and Bruce, {Elliott L.} and Malavika Manoj and Yuanyuan Du and Dawson, {Daniel M.} and Ashbrook, {Sharon E.} and Cox, {Paul A.} and Wright, {Paul A.}",

note = "Funding: The authors thank the EPSRC (Designed Synthesis of Zeolites (EP/S016201/1 (PAW, MML), EP/S016147/1, PAC)) and Orbital Materials (PAW, RGC) for funding. They acknowledge the SEM-EDS and Raman spectroscopy equipment funding (EPSRC Capital for Great Technologies Grant: EP/L017008/1; EPSRC Light Element Analysis Facility Grant: EP/T019298/1; EPSRC Strategic Equipment Resource Grant: EP/R023751/1) and EPSRC Core Equipment Grant (EP/V034138/1).",

year = "2025",

month = may,

day = "7",

doi = "10.1002/chem.202500327",

language = "English",

volume = "Early View",

journal = "Chemistry - A European Journal",

issn = "0947-6539",

publisher = "John Wiley & Sons, Ltd",

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TY - JOUR

T1 - In situ generation by cyclization of an organic structure directing agent for the synthesis of high silica zeolite ERS-7

AU - Lozinska, Magdalena M.

AU - Chitac, Ruxandra G.

AU - Bruce, Elliott L.

AU - Manoj, Malavika

AU - Du, Yuanyuan

AU - Dawson, Daniel M.

AU - Ashbrook, Sharon E.

AU - Cox, Paul A.

AU - Wright, Paul A.

N1 - Funding: The authors thank the EPSRC (Designed Synthesis of Zeolites (EP/S016201/1 (PAW, MML), EP/S016147/1, PAC)) and Orbital Materials (PAW, RGC) for funding. They acknowledge the SEM-EDS and Raman spectroscopy equipment funding (EPSRC Capital for Great Technologies Grant: EP/L017008/1; EPSRC Light Element Analysis Facility Grant: EP/T019298/1; EPSRC Strategic Equipment Resource Grant: EP/R023751/1) and EPSRC Core Equipment Grant (EP/V034138/1).

PY - 2025/5/7

Y1 - 2025/5/7

N2 - Zeolites with high framework Si/Al ratios are of interest for industrial applications due to their hydrothermal stability. They are usually synthesized in the presence of pre-prepared organic structure directing agents (OSDAs). The high silica ERS-7 zeolite (topology type ESV) can be crystallized using N,N-dimethylpyrrolidinium (dmpyrr) that is formed in situ via cyclization of N,N,N’,N’-tetramethyl-1,4-diaminobutane (tmdab) when a cationic polymer is also present. The in situ generation of dmpyrr is demonstrated by solid-state 13C NMR spectroscopy and supported by both chemical analyses and comparative syntheses using pre-prepared dmpyrr. The cationic polymer inhibits the crystallization of mordenite, which is otherwise observed to be the favored product. The ERS-7 prepared via in situ dmpyrr synthesis (Si/Al = 14) is characterized by PXRD and solid-state NMR spectroscopy. The CO2 adsorption seen for the H- and Na-forms indicates interactions with accessible Na+ cations. The synthetic studies indicate the potential for in situ generation of OSDAs to reduce the need for extended OSDA syntheses.

AB - Zeolites with high framework Si/Al ratios are of interest for industrial applications due to their hydrothermal stability. They are usually synthesized in the presence of pre-prepared organic structure directing agents (OSDAs). The high silica ERS-7 zeolite (topology type ESV) can be crystallized using N,N-dimethylpyrrolidinium (dmpyrr) that is formed in situ via cyclization of N,N,N’,N’-tetramethyl-1,4-diaminobutane (tmdab) when a cationic polymer is also present. The in situ generation of dmpyrr is demonstrated by solid-state 13C NMR spectroscopy and supported by both chemical analyses and comparative syntheses using pre-prepared dmpyrr. The cationic polymer inhibits the crystallization of mordenite, which is otherwise observed to be the favored product. The ERS-7 prepared via in situ dmpyrr synthesis (Si/Al = 14) is characterized by PXRD and solid-state NMR spectroscopy. The CO2 adsorption seen for the H- and Na-forms indicates interactions with accessible Na+ cations. The synthetic studies indicate the potential for in situ generation of OSDAs to reduce the need for extended OSDA syntheses.

KW - Cationic polymer

KW - ESV topology type

KW - In situ OSDA formation

KW - Zeolite synthesis

U2 - 10.1002/chem.202500327

DO - 10.1002/chem.202500327

M3 - Article

SN - 0947-6539

VL - Early View

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

M1 - e202500327

ER -

In situ generation by cyclization of an organic structure directing agent for the synthesis of high silica zeolite ERS-7

Abstract

Keywords

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Projects

Light Element Analysis Facility (LEAF): Light Element Analysis Facility (LEAF)

Designed Synthesis of Zeolites for Envir: Designed Synthesis of Zeolites for Environmental and Biorenewables Catalysis

Electon Microscopy: Electon Microscopy for the characterisation and manipulation of advanced function materials and their interfaces at the nanoscale

Datasets

In Situ Generation by Cyclisation of an Organic Structure Directing Agent for the Synthesis of High Silica Zeolite ERS-7 (dataset)

Cite this