The force of MOFs: the potential of switchable metal–organic frameworks as solvent stimulated actuators

Freund, Pascal; Senkovska, Irena; Zheng, Bin; Bon, Volodymyr; Krause, Beate; Maurin, Guillaume; Kaskel, Stefan

doi:10.1039/d0cc02505d

Cited by 18 publications

(19 citation statements)

References 32 publications

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“…In this context hydrostatic pressure as external stimulus is gaining more and more attention, [23, 24] providing fundamental insight into the microscopic chemical interactions as reflected in the macroscopic mechanical properties. Furthermore, studies on the high‐pressure structural behaviour address application‐oriented aspects of MOFs such as stability concerns during material shaping, extrusion and pellet formation for catalytic processes [25, 26] and their potential as shock absorbers and dampers [27–30] . A few well‐studied examples are MIL‐53 and MIL‐47 (MIL=Matériaux de l'Institut Lavoisier; MIL‐47: V(O)(bdc); MIL‐53: M(OH)(bdc); M 3+ =Al 3+ , Fe 3+ , Cr 3+ , bdc 2− =1,4‐benzenedicarboxylate), [31–34] which are based on a winerack‐type structure motif.…”

Section: Introductionmentioning

confidence: 99%

“…Furthermore, studies on the highpressure structural behaviour address application-oriented aspects of MOFs such as stability concerns during material shaping, extrusion and pellet formation for catalytic processes [25,26] and their potential as shock absorbers and damp-ers. [27][28][29][30] A few well-studied examples are MIL-53 and MIL-47 (MIL = MatØriaux de lInstitut Lavoisier; MIL-47: V(O)-(bdc); MIL-53: M(OH)(bdc); M 3+ = Al 3+ , Fe 3+ , Cr 3+ , bdc 2À = 1,4-benzenedicarboxylate), [31][32][33][34] which are based on a winerack-type structure motif. When applying hydrostatic pressure to MIL-53 and MIL-47, both materials show a large pore (lp) to narrow pore (np) phase transition.…”

Section: Introductionmentioning

confidence: 99%

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Configurational Entropy Driven High‐Pressure Behaviour of a Flexible Metal–Organic Framework (MOF)

et al. 2020

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Flexible metal-organic frameworks (MOFs) show large structural flexibility as a function of temperature or (gas)pressure variation, a fascinating property of high technological and scientific relevance. The targeted design of flexible MOFs demands control over the macroscopic thermodynamics as determined by microscopic chemical interactions and remains an open challenge. Herein we apply high-pressure powder X-ray diffraction and molecular dynamics simulations to gain insight into the microscopic chemical factors that determine the high-pressure macroscopic thermodynamics of two flexible pillared-layer MOFs. For the first time we identify configurational entropy that originates from side-chain modifications of the linker as the key factor determining the thermodynamics in a flexible MOF. The study shows that configurational entropy is an important yet largely overlooked parameter, providing an intriguing perspective of how to chemically access the underlying free energy landscape in MOFs.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Configurational Entropy Driven High‐Pressure Behaviour of a Flexible Metal–Organic Framework (MOF)

et al. 2020

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“…It is noted that the stress on the MIL‐53(Al)‐NaCl mixture significantly increased as the gas was dosed. Indeed, the swelling of MIL‐53(Al) upon guest uptake is known to exert a significant force on a constrained system [37] . Subsequently, P gas runs at a single cell compression state have been selected to explore the effect of σ mech on the structural transformations undergone by the MOF, which are presented in Figure 3b–d.…”

Section: Figurementioning

confidence: 99%

“…Indeed, the swelling of MIL-53(Al) upon guest uptake is known to exert a significant force on a constrained system. [37] Subsequently, P gas runs at a single cell compression state have been selected to explore the effect of σ mech on the structural…”

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confidence: 99%

Structural Insight of MOFs under Combined Mechanical and Adsorption Stimuli

Iacomi

Alabarse

Appleyard³

et al. 2022

Angewandte Chemie

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External control over the pore size of flexible metal-organic frameworks (MOFs) has recently emerged as an intriguing concept, with possible applications to gas storage and separation. In this work we present a new pressure cell capable for the first time of monitoring through in situ X-ray powder diffraction an adsorbent powder under combined uniaxial applied mechanical stress (up to 1 GPa) and gas pressure (up to 20 bar). The combined stress-pressure clamp (CSPC) cell was successfully exploited to follow the evolution of the CO 2 breathing behaviour of the prototypical complex breathing MIL-53(Al) system under mechanical compression obtaining structural evidence that this MOF can be maintained in its closed pore state upon compression, precluding its re-opening at high gas pressure (> 7 bar). This novel setup shows potential for the in-operando exploration of flexible systems, in equilibrium and flow configurations.Soft crystalline porous materials, such as metal-organic frameworks (MOFs) which can undergo substantial structural changes under the application of a variety of stimuli, have attracted significant scientific interest. [1][2][3] This is, in part, due to the promise they hold for unprecedented performance in applications like gas storage, gas separation, catalysis and sensing, [4][5][6][7] but also due to compelling prospects as molecular-level factories or nanomachines. [8] In this family of materials, structural dynamics can be induced by the uptake of various molecular probes in the framework pores or by the application of other stimuli, with temperature, external stress, electromagnetic radiation, electric or magnetic fields, just to name a few. [1][2][3]

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“…6,7 Subsequent investigations uncovered not only a variety of flexible PCPs 8−11 but also other flexible materials, covalent organic frameworks, 12 which are promising materials with potential applications as components of highly efficient gas separation, 13 sensor, 14 and actuator systems. 15 Most flexible PCPs undergo a structural change, in which pore opening takes place permanently in conjunction with guest uptake (type a, Figure 1a). In contrast, only a few PCPs have flexible structures that undergo temporary pore opening during guest adsorption/desorption (type b, Figure 1b).…”

Section: ■ Introductionmentioning

confidence: 99%

A Temporarily Pore-Openable Porous Coordination Polymer for Guest Adsorption/Desorption

Noro

Suzuki

et al. 2021

Inorg. Chem.

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Flexible porous coordination polymers (PCPs)/ metal−organic frameworks are unique materials that have potential applications as components of highly efficient separation, sensor, and actuator systems. In general, the structures of flexible PCPs drastically change upon guest loading. In this investigation, we uncovered the rare one-dimensional PCP [Cu 2 (bza) 4 (2-apyr)] (1; bza = benzoate and 2-apyr = 2-aminopyrimidine), which exhibits a unique type of flexibility involving temporary pore opening. Singlecrystal X-ray diffraction analysis revealed that desolvated 1 and ethyl acetate (AcOEt)-loaded (1•AcOEt) and CO 2 -loaded (1• CO 2 ) 1 have isolated pores. In the case of 1, the pore structure prevents guest penetration. In addition, the isolated pore structures of 1•AcOEt and 1•CO 2 block guest release. However, 1 participates in reversible adsorption/desorption of AcOEt and CO 2 because pore opening occurs temporarily. The CO 2 adsorption/desorption isotherms of 1 are type I and dissimilar to those observed in traditional flexible PCPs with adsorption/desorption hysteresis. The lesser conventional flexibility displayed by 1 could offer new insight into the design of flexible PCPs.

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The force of MOFs: the potential of switchable metal–organic frameworks as solvent stimulated actuators

Abstract:
The force exerted by flexible metal–organic framework through expansion was experimentally evaluated for MIL-53(Al).

Cited by 18 publications

References 32 publications

Configurational Entropy Driven High‐Pressure Behaviour of a Flexible Metal–Organic Framework (MOF)

Configurational Entropy Driven High‐Pressure Behaviour of a Flexible Metal–Organic Framework (MOF)

Structural Insight of MOFs under Combined Mechanical and Adsorption Stimuli

A Temporarily Pore-Openable Porous Coordination Polymer for Guest Adsorption/Desorption

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The force of MOFs: the potential of switchable metal–organic frameworks as solvent stimulated actuators

Abstract: The force exerted by flexible metal–organic framework through expansion was experimentally evaluated for MIL-53(Al).

Cited by 18 publications

References 32 publications

Configurational Entropy Driven High‐Pressure Behaviour of a Flexible Metal–Organic Framework (MOF)

Configurational Entropy Driven High‐Pressure Behaviour of a Flexible Metal–Organic Framework (MOF)

Structural Insight of MOFs under Combined Mechanical and Adsorption Stimuli

A Temporarily Pore-Openable Porous Coordination Polymer for Guest Adsorption/Desorption

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Abstract:
The force exerted by flexible metal–organic framework through expansion was experimentally evaluated for MIL-53(Al).