Preventing undesirable structure flexibility in pyromellitate metal organic frameworks

Oliver G Hayes; Stewart James Warrender; David B. Cordes; Morven J. Duncan; Alexandra M. Z. Slawin; Russell E. Morris

doi:10.1002/ejic.202000322

Preventing undesirable structure flexibility in pyromellitate metal organic frameworks

Oliver G Hayes, Stewart James Warrender, David B. Cordes, Morven J. Duncan, Alexandra M. Z. Slawin, Russell E. Morris

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

Abstract

Removal of coordinated water molecules from the porous Zn‐pyromellitate metal organic framework Zn₅(OH)₂(PMA)₂(H₂O)₄· x H₂O (PMA = pyromellitic acid or 1,2,4,5‐benzene tetracarboxylic acid) should generate coordinatively unsaturated metal sites suitable for gas adsorption. However, reports of instability towards dehydration have restricted the study and utility of this MOF. Here we examine in more detail the nature of the structural transformation that occurs upon dehydration. This study reveals that a fully reversible crystalline‐crystalline transformation from a porous to a non‐porous homologue takes place, proceeding through a partially dehydrated intermediate. We show that doping the structure with Ni²⁺ ions at greater than 30 % prevents structural rearrangement, thereby maintaining porosity, and rendering the material effective for gas (nitric oxide) adsorption applications. These results indicate that doping can be an effective means to increase the utility of otherwise unserviceable structures.

Original language	English
Pages (from-to)	2537-2544
Number of pages	8
Journal	European Journal of Inorganic Chemistry
Volume	2020
Issue number	26
Early online date	27 May 2020
DOIs	https://doi.org/10.1002/ejic.202000322
Publication status	Published - 15 Jul 2020

Keywords

Crystalline-crystalline transformation
Doping
Metal-organic frameworks
Nitric oxide
Structure elucidation

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10.1002/ejic.202000322Licence: CC BY

Hayes_2020_EJIC_MOF_CC
Copyright © 2020 The Authors. Published by Wiley‐VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.
Final published version, 1.79 MBLicence: CC BY

ProDIA: Production, control and Demonstration of structured hybrid nanoporous materials for Industrial adsorption Applications
Morris, R. E. (PI)
European Commission
1/11/15 → 31/10/18
Project: Standard
Hemilabile switchable metal-organic: Hemilabile and switchable metal-organic frameworks
Morris, R. E. (PI)
EPSRC
1/03/13 → 28/02/16
Project: Standard
Structuring the Future: Structuring the Future - Underpinning world-leading science in EaStCHEM through cutting edge characterisation
Woollins, J. D. (PI), Ashbrook, S. E. (CoI), Morris, R. E. (CoI) & Slawin, A. M. Z. (CoI)
EPSRC
1/01/13 → 31/03/13
Project: Standard

Cite this

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title = "Preventing undesirable structure flexibility in pyromellitate metal organic frameworks",

abstract = "Removal of coordinated water molecules from the porous Zn‐pyromellitate metal organic framework Zn5(OH)2(PMA)2(H2O)4· x H2O (PMA = pyromellitic acid or 1,2,4,5‐benzene tetracarboxylic acid) should generate coordinatively unsaturated metal sites suitable for gas adsorption. However, reports of instability towards dehydration have restricted the study and utility of this MOF. Here we examine in more detail the nature of the structural transformation that occurs upon dehydration. This study reveals that a fully reversible crystalline‐crystalline transformation from a porous to a non‐porous homologue takes place, proceeding through a partially dehydrated intermediate. We show that doping the structure with Ni2+ ions at greater than 30 % prevents structural rearrangement, thereby maintaining porosity, and rendering the material effective for gas (nitric oxide) adsorption applications. These results indicate that doping can be an effective means to increase the utility of otherwise unserviceable structures.",

keywords = "Crystalline-crystalline transformation, Doping, Metal-organic frameworks, Nitric oxide, Structure elucidation",

author = "Hayes, {Oliver G} and Warrender, {Stewart James} and Cordes, {David B.} and Duncan, {Morven J.} and Slawin, {Alexandra M. Z.} and Morris, {Russell E.}",

note = "This project has received funding from: the European Union's Horizon 2020 research and innovation program under grant agreement No 685727; the Engineering & Physical Sciences Research Council (EPSRC) under awards EP/K005499/1 and EP/K039210/1; and the University of St Andrews School of Chemistry.",

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doi = "10.1002/ejic.202000322",

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pages = "2537--2544",

journal = "European Journal of Inorganic Chemistry",

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T1 - Preventing undesirable structure flexibility in pyromellitate metal organic frameworks

AU - Hayes, Oliver G

AU - Warrender, Stewart James

AU - Cordes, David B.

AU - Duncan, Morven J.

AU - Slawin, Alexandra M. Z.

AU - Morris, Russell E.

N1 - This project has received funding from: the European Union's Horizon 2020 research and innovation program under grant agreement No 685727; the Engineering & Physical Sciences Research Council (EPSRC) under awards EP/K005499/1 and EP/K039210/1; and the University of St Andrews School of Chemistry.

PY - 2020/7/15

Y1 - 2020/7/15

N2 - Removal of coordinated water molecules from the porous Zn‐pyromellitate metal organic framework Zn5(OH)2(PMA)2(H2O)4· x H2O (PMA = pyromellitic acid or 1,2,4,5‐benzene tetracarboxylic acid) should generate coordinatively unsaturated metal sites suitable for gas adsorption. However, reports of instability towards dehydration have restricted the study and utility of this MOF. Here we examine in more detail the nature of the structural transformation that occurs upon dehydration. This study reveals that a fully reversible crystalline‐crystalline transformation from a porous to a non‐porous homologue takes place, proceeding through a partially dehydrated intermediate. We show that doping the structure with Ni2+ ions at greater than 30 % prevents structural rearrangement, thereby maintaining porosity, and rendering the material effective for gas (nitric oxide) adsorption applications. These results indicate that doping can be an effective means to increase the utility of otherwise unserviceable structures.

AB - Removal of coordinated water molecules from the porous Zn‐pyromellitate metal organic framework Zn5(OH)2(PMA)2(H2O)4· x H2O (PMA = pyromellitic acid or 1,2,4,5‐benzene tetracarboxylic acid) should generate coordinatively unsaturated metal sites suitable for gas adsorption. However, reports of instability towards dehydration have restricted the study and utility of this MOF. Here we examine in more detail the nature of the structural transformation that occurs upon dehydration. This study reveals that a fully reversible crystalline‐crystalline transformation from a porous to a non‐porous homologue takes place, proceeding through a partially dehydrated intermediate. We show that doping the structure with Ni2+ ions at greater than 30 % prevents structural rearrangement, thereby maintaining porosity, and rendering the material effective for gas (nitric oxide) adsorption applications. These results indicate that doping can be an effective means to increase the utility of otherwise unserviceable structures.

KW - Crystalline-crystalline transformation

KW - Doping

KW - Metal-organic frameworks

KW - Nitric oxide

KW - Structure elucidation

U2 - 10.1002/ejic.202000322

DO - 10.1002/ejic.202000322

M3 - Article

SN - 1434-1948

VL - 2020

SP - 2537

EP - 2544

JO - European Journal of Inorganic Chemistry

JF - European Journal of Inorganic Chemistry

IS - 26

ER -

Preventing undesirable structure flexibility in pyromellitate metal organic frameworks

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Keywords

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Projects

ProDIA: Production, control and Demonstration of structured hybrid nanoporous materials for Industrial adsorption Applications

Hemilabile switchable metal-organic: Hemilabile and switchable metal-organic frameworks

Structuring the Future: Structuring the Future - Underpinning world-leading science in EaStCHEM through cutting edge characterisation

Cite this