Pressure-induced symmetry changes in body-centred cubic zeolites

Antony Nearchou; Mero Lee U. Cornelius; Zöe L. Jones1; I. E. Collings; Stephen A. Wells; Paul R. Raithby; Asel Sartbaeva

doi:10.1098/rsos.182158

Pressure-induced symmetry changes in body-centred cubic zeolites

Antony Nearchou, Mero Lee U. Cornelius, Zöe L. Jones1, I. E. Collings, Stephen A. Wells, Paul R. Raithby, Asel Sartbaeva

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

13 Citations (SciVal)

Abstract

Previous work has shown a strong correlation between zeolite framework flexibility and the nature of structural symmetry and phase transitions. However, there is little experimental data regarding this relationship, in addition to how flexibility can be connected to the synthesis of these open-framework materials. This is of interest for the synthesis of novel zeolites, which require organic additives to permutate the resulting geometry and symmetry of the framework. Here, we have used high-pressure powder X-ray diffraction to study the three zeolites: Na-X, RHO and ZK-5, which can all be prepared using 18-crown-6 ether as an organic additive. We observe significant differences in how the occluded 18-crown-6 ether influences the framework flexibility-this being dependent on the geometry of the framework. We use these differences as an indicator to define the role of 18-crown-6 ether during zeolite crystallization. Furthermore, in conjunction with previous work, we predict that pressureinduced symmetry transitions are intrinsic to body-centred cubic zeolites. The high symmetry yields fewer degrees of freedom, meaning it is energetically favourable to lower the symmetry to facilitate further compression.

Original language	English
Article number	182158
Pages (from-to)	1-15
Number of pages	15
Journal	Royal Society Open Science
Volume	6
Issue number	7
DOIs	https://doi.org/10.1098/rsos.182158
Publication status	Published - 24 Jul 2019

Funding

Data accessibility. All data created during this study are available free of charge from the University of Bath data archive at https://doi.org/10.15125/BATH-00580 [58]. Authors’ contributions. The study was conceived by A.S. and A.N. The data were collected by A.N., M-L.U.C., Z.L.J. and A.S. with the assistance of I.E.C. on the ID15B beamline at the ESRF. The geometric simulations in GASP were performed by M-L.U.C. Pawley refinements using the TOPAS Academic software were undertaken by A.N. All authors, including S.A.W. and P.R.R., were involved in the data interpretation and editing of the manuscript. The original manuscript was written by A.N., with input and approval from all authors. All authors gave final approval for publication. Competing interests. We declare we have no competing interests. Funding. This study was funded by the Royal Society under the ‘New flexible frameworks for catalysis, energy materials and nanotechnology’ URF grant awarded to A.S. Further funding was contributed by the EPSRC under the EP/ K004956/1 grant, of whom P.R.R. is the principal investigator. S.A.W. acknowledges funding from the ERC under the European Union’s Horizon 2020 Research and Innovation Programme (grant agreement no. 648283 ‘GROWMOF’). M-L.U.C. would like to thank the National Research Foundation of South Africa for funding the research project and the Commonwealth Scholarship Commission in the United Kingdom for funding the research visit to the University of Bath, United Kingdom. Acknowledgements. The high-pressure X-ray diffraction data herein was collected on beamline ID15B at the European Synchrotron Radiation Facility (ESRF), Grenoble, France. We thank the ESRF Council for accepting our research proposal.

Keywords

Cubic
High pressure
Phase transition
Symmetry
X-ray diffraction
Zeolite

ASJC Scopus subject areas

General

Access to Document

10.1098/rsos.182158Licence: CC BY

Cite this

@article{441b6b00ac0d4c41b43d60b6347b8d8f,

title = "Pressure-induced symmetry changes in body-centred cubic zeolites",

abstract = "Previous work has shown a strong correlation between zeolite framework flexibility and the nature of structural symmetry and phase transitions. However, there is little experimental data regarding this relationship, in addition to how flexibility can be connected to the synthesis of these open-framework materials. This is of interest for the synthesis of novel zeolites, which require organic additives to permutate the resulting geometry and symmetry of the framework. Here, we have used high-pressure powder X-ray diffraction to study the three zeolites: Na-X, RHO and ZK-5, which can all be prepared using 18-crown-6 ether as an organic additive. We observe significant differences in how the occluded 18-crown-6 ether influences the framework flexibility-this being dependent on the geometry of the framework. We use these differences as an indicator to define the role of 18-crown-6 ether during zeolite crystallization. Furthermore, in conjunction with previous work, we predict that pressureinduced symmetry transitions are intrinsic to body-centred cubic zeolites. The high symmetry yields fewer degrees of freedom, meaning it is energetically favourable to lower the symmetry to facilitate further compression.",

keywords = "Cubic, High pressure, Phase transition, Symmetry, X-ray diffraction, Zeolite",

author = "Antony Nearchou and Cornelius, {Mero Lee U.} and Jones1, {Z{\"o}e L.} and Collings, {I. E.} and Wells, {Stephen A.} and Raithby, {Paul R.} and Asel Sartbaeva",

year = "2019",

month = jul,

day = "24",

doi = "10.1098/rsos.182158",

language = "English",

volume = "6",

pages = "1--15",

journal = "Royal Society Open Science",

issn = "2054-5703",

publisher = "The Royal Society",

number = "7",

}

TY - JOUR

T1 - Pressure-induced symmetry changes in body-centred cubic zeolites

AU - Nearchou, Antony

AU - Cornelius, Mero Lee U.

AU - Jones1, Zöe L.

AU - Collings, I. E.

AU - Wells, Stephen A.

AU - Raithby, Paul R.

AU - Sartbaeva, Asel

PY - 2019/7/24

Y1 - 2019/7/24

N2 - Previous work has shown a strong correlation between zeolite framework flexibility and the nature of structural symmetry and phase transitions. However, there is little experimental data regarding this relationship, in addition to how flexibility can be connected to the synthesis of these open-framework materials. This is of interest for the synthesis of novel zeolites, which require organic additives to permutate the resulting geometry and symmetry of the framework. Here, we have used high-pressure powder X-ray diffraction to study the three zeolites: Na-X, RHO and ZK-5, which can all be prepared using 18-crown-6 ether as an organic additive. We observe significant differences in how the occluded 18-crown-6 ether influences the framework flexibility-this being dependent on the geometry of the framework. We use these differences as an indicator to define the role of 18-crown-6 ether during zeolite crystallization. Furthermore, in conjunction with previous work, we predict that pressureinduced symmetry transitions are intrinsic to body-centred cubic zeolites. The high symmetry yields fewer degrees of freedom, meaning it is energetically favourable to lower the symmetry to facilitate further compression.

AB - Previous work has shown a strong correlation between zeolite framework flexibility and the nature of structural symmetry and phase transitions. However, there is little experimental data regarding this relationship, in addition to how flexibility can be connected to the synthesis of these open-framework materials. This is of interest for the synthesis of novel zeolites, which require organic additives to permutate the resulting geometry and symmetry of the framework. Here, we have used high-pressure powder X-ray diffraction to study the three zeolites: Na-X, RHO and ZK-5, which can all be prepared using 18-crown-6 ether as an organic additive. We observe significant differences in how the occluded 18-crown-6 ether influences the framework flexibility-this being dependent on the geometry of the framework. We use these differences as an indicator to define the role of 18-crown-6 ether during zeolite crystallization. Furthermore, in conjunction with previous work, we predict that pressureinduced symmetry transitions are intrinsic to body-centred cubic zeolites. The high symmetry yields fewer degrees of freedom, meaning it is energetically favourable to lower the symmetry to facilitate further compression.

KW - Cubic

KW - High pressure

KW - Phase transition

KW - Symmetry

KW - X-ray diffraction

KW - Zeolite

UR - http://www.scopus.com/inward/record.url?scp=85070775707&partnerID=8YFLogxK

U2 - 10.1098/rsos.182158

DO - 10.1098/rsos.182158

M3 - Article

AN - SCOPUS:85070775707

SN - 2054-5703

VL - 6

SP - 1

EP - 15

JO - Royal Society Open Science

JF - Royal Society Open Science

IS - 7

M1 - 182158

ER -

Pressure-induced symmetry changes in body-centred cubic zeolites

Abstract

Funding

Keywords

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Transfer from Oxford to Bath of RS Fellowship

Applying Long-Lived Metastable States in Switchable Functionality via Kinetic Control of Molecular Assembly

Dataset for "Pressure-induced symmetry changes in body-centred cubic zeolites"

Cite this

Pressure-induced symmetry changes in body-centred cubic zeolites

Abstract

Funding

Keywords

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Projects

Transfer from Oxford to Bath of RS Fellowship

Applying Long-Lived Metastable States in Switchable Functionality via Kinetic Control of Molecular Assembly

Datasets

Dataset for "Pressure-induced symmetry changes in body-centred cubic zeolites"

Cite this