Temperature dependence of adsorption hysteresis in flexible metal organic frameworks

© 2020, The Author(s). “Breathing” and “gating” are striking phenomena exhibited by flexible metal-organic frameworks (MOFs) in which their pore structures transform upon external stimuli. These effects are often associated with eminent steps and hysteresis in sorption isotherms. Despite signifi...

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Main Authors: Rahman, S., Arami-Niya, Arash, Yang, X., Xiao, G., Li, G., May, E.F.
Format: Journal Article
Language:English
Published: NATURE RESEARCH 2020
Subjects:
Online Access:http://purl.org/au-research/grants/arc/IC150100019
http://hdl.handle.net/20.500.11937/82395
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author Rahman, S.
Arami-Niya, Arash
Yang, X.
Xiao, G.
Li, G.
May, E.F.
author_facet Rahman, S.
Arami-Niya, Arash
Yang, X.
Xiao, G.
Li, G.
May, E.F.
author_sort Rahman, S.
building Curtin Institutional Repository
collection Online Access
description © 2020, The Author(s). “Breathing” and “gating” are striking phenomena exhibited by flexible metal-organic frameworks (MOFs) in which their pore structures transform upon external stimuli. These effects are often associated with eminent steps and hysteresis in sorption isotherms. Despite significant mechanistic studies, the accurate description of stepped isotherms and hysteresis remains a barrier to the promised applications of flexible MOFs in molecular sieving, storage and sensing. Here, we investigate the temperature dependence of structural transformations in three flexible MOFs and present a new isotherm model to consistently analyse the transition pressures and step widths. The transition pressure reduces exponentially with decreasing temperature as does the degree of hysteresis (c.f. capillary condensation). The MOF structural transition enthalpies range from +6 to +31 kJ·mol−1 revealing that the adsorption-triggered transition is entropically driven. Pressure swing adsorption process simulations based on flexible MOFs that utilise the model reveal how isotherm hysteresis can affect separation performance.
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spelling curtin-20.500.11937-823952021-03-02T04:22:48Z Temperature dependence of adsorption hysteresis in flexible metal organic frameworks Rahman, S. Arami-Niya, Arash Yang, X. Xiao, G. Li, G. May, E.F. Science & Technology Physical Sciences Chemistry, Multidisciplinary Chemistry STRUCTURAL TRANSITIONS CO2 STORAGE CH4 THERMODYNAMICS PREDICTION BEHAVIOR ZIF-7 © 2020, The Author(s). “Breathing” and “gating” are striking phenomena exhibited by flexible metal-organic frameworks (MOFs) in which their pore structures transform upon external stimuli. These effects are often associated with eminent steps and hysteresis in sorption isotherms. Despite significant mechanistic studies, the accurate description of stepped isotherms and hysteresis remains a barrier to the promised applications of flexible MOFs in molecular sieving, storage and sensing. Here, we investigate the temperature dependence of structural transformations in three flexible MOFs and present a new isotherm model to consistently analyse the transition pressures and step widths. The transition pressure reduces exponentially with decreasing temperature as does the degree of hysteresis (c.f. capillary condensation). The MOF structural transition enthalpies range from +6 to +31 kJ·mol−1 revealing that the adsorption-triggered transition is entropically driven. Pressure swing adsorption process simulations based on flexible MOFs that utilise the model reveal how isotherm hysteresis can affect separation performance. 2020 Journal Article http://hdl.handle.net/20.500.11937/82395 10.1038/s42004-020-00429-3 English http://purl.org/au-research/grants/arc/IC150100019 http://purl.org/au-research/grants/arc/DP190100983 http://creativecommons.org/licenses/by/4.0/ NATURE RESEARCH fulltext
spellingShingle Science & Technology
Physical Sciences
Chemistry, Multidisciplinary
Chemistry
STRUCTURAL TRANSITIONS
CO2
STORAGE
CH4
THERMODYNAMICS
PREDICTION
BEHAVIOR
ZIF-7
Rahman, S.
Arami-Niya, Arash
Yang, X.
Xiao, G.
Li, G.
May, E.F.
Temperature dependence of adsorption hysteresis in flexible metal organic frameworks
title Temperature dependence of adsorption hysteresis in flexible metal organic frameworks
title_full Temperature dependence of adsorption hysteresis in flexible metal organic frameworks
title_fullStr Temperature dependence of adsorption hysteresis in flexible metal organic frameworks
title_full_unstemmed Temperature dependence of adsorption hysteresis in flexible metal organic frameworks
title_short Temperature dependence of adsorption hysteresis in flexible metal organic frameworks
title_sort temperature dependence of adsorption hysteresis in flexible metal organic frameworks
topic Science & Technology
Physical Sciences
Chemistry, Multidisciplinary
Chemistry
STRUCTURAL TRANSITIONS
CO2
STORAGE
CH4
THERMODYNAMICS
PREDICTION
BEHAVIOR
ZIF-7
url http://purl.org/au-research/grants/arc/IC150100019
http://purl.org/au-research/grants/arc/IC150100019
http://hdl.handle.net/20.500.11937/82395