Tolerance of Flexible MOFs toward Repeated Adsorption Stress

Bon, Volodymyr; Kavoosi, Negar; Senkovska, Irena; Kaskel, Stefan

doi:10.1021/acsami.5b05456

Cited by 78 publications

(90 citation statements)

References 35 publications

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“…Their functional exploitation, however, remains challenging owing to the lack of design criteria for switchable MOFs . Moreover, switchability cycling after exposure to water or repeated adsorption and desorption stress pose significant limitations . Rare examples of flexible, yet very stable MOFs include recent zirconium frameworks as well as the prominent breathing MIL‐53 and swelling MIL‐88 …”

Section: Introductionmentioning

confidence: 99%

Collective Breathing in an Eightfold Interpenetrated Metal–Organic Framework: From Mechanistic Understanding towards Threshold Sensing Architectures

et al. 2020

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Functional materials that respond to chemical or physical stimuli through reversible structural transformations are highly desirable for the integration into devices. Now, a new stable and flexible eightfold interpenetrated three‐dimensional (3D) metal–organic framework (MOF) is reported, [Zn(oba)(pip)]n (JUK‐8) based on 4,4′‐oxybis(benzenedicarboxylate) (oba) and 4‐pyridyl functionalized benzene‐1,3‐dicarbohydrazide (pip) linkers, featuring distinct switchability in response to guest molecules (H2O and CO2) or temperature. Single‐crystal X‐ray diffraction (SC‐XRD), combined with density functional theory (DFT) and grand canonical Monte Carlo (GCMC) simulations, reveal a unique breathing mechanism involving collective motions of eight mixed‐linker diamondoid subnetworks with only minor displacements between them. The pronounced stepwise volume change of JUK‐8 during water adsorption is used to construct an electron conducting composite film for resistive humidity sensing.

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Section: Introductionmentioning

confidence: 99%

Collective Breathing in an Eightfold Interpenetrated Metal–Organic Framework: From Mechanistic Understanding towards Threshold Sensing Architectures

et al. 2020

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“…Perpendicular wine-rack modes also provide explanation of observed single-crystal breakage during op-cl transformation. [40] Furthermore, our results suggest that the structural features imposed by a single-unit cell view of the structure should be revisited.…”

Section: Discussionmentioning

confidence: 92%

“…[22] The forming of this type of domains also correlates with the experimental observation, that crystal-breakage during adsorptiondesorption cycles primarily occurs along the crystallographic C direction (along pillars). [40] These systems can either remain in a partially open form, distort the PWs in the interface regions or one of the domains spontaneously reopens and closes again to yield a pure conformer. Higher temperatures are expected to favor the latter, higher pres-sures the former.…”

Section: Structurementioning

confidence: 99%

A Ligand Field Molecular Mechanics Study of CO₂‐Induced Breathing in the Metal–Organic Framework DUT‐8(Ni)

Melix

Paesani

Heine

2019

Advcd Theory and Sims

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Flexible metal-organic Frameworks (MOFs) are an interesting class of materials due to their diverse properties. One representative of this class is the layered-pillar MOF DUT-8(Ni). This MOF consists of Ni 2 paddle wheels interconnected by naphthalene dicarboxylate linkers and dabco pillars (Ni 2 (ndc) 2 (dabco), ndc = 2,6-naphthalene-dicarboxylate, dabco = 1,4-diazabicyclo-[2.2.2]-octane). DUT-8(Ni) undergoes a volume change of over 140% upon adsorption of guest molecules. Herein, a ligand field molecular mechanics (LFMM) study of the CO 2 -induced flexibility of DUT-8(Ni) is presented. LFMM is able to reproduce experimental and DFT structural features as well as properties that require large simulation cells. It is shown that the transformation energy from a closed to open state of the MOF is overcompensated fivefold by the host-guest interactions. Structural characteristics of the MOF explain the shape of the energy profile at different loading states and provide useful insights to the interpretation of previous experimental results.the possibilities of employing ligand field molecular mechanics (LFMM) simulations to study flexible MOFs and their processes. The method employed is not limited to adsorption processes but as has been shown previously [8][9][10][11] to be applicable to other properties, for example, spin states or magnetic properties. Our goal is to present simulations using the example of CO 2induced breathing in the pillared layer MOF DUT-8(Ni) [12] (Ni 2 (ndc) 2 (dabco), ndc = 2,6naphthalenedicarboxylate, dabco = 1,4diazabicyclo-[2.2.2]-octane, see Figure 1) using an LFMM approach. Motivated by its outstanding properties, DUT-8(Ni) is being investigated extensively recently. [12][13][14][15][16][17][18][19][20][21][22][23] Some examples of the properties of interest are the enormous volume change upon opening (more than 140 %), [14] its isomorphism, [22] the property dependence on the metal center, [14] and crystallite size effects. [19] Alzahrani and Deeth [24] already employed LFMM to investigate clusters of Zn 2 (bdc) 2 (dabco) and showed the applicability to this structurally related flexible MOF. We present here the first application of LFMM to simulate the breathing of an openshell transition-metal paddle wheel pillared layer MOF in periodic boundary conditions.

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“…While X‐pcu‐5‐Zn exhibited structural transformation across three phases, X‐pcu‐6‐Zn only cycles between the α and β phases. The fact that the related pillared‐layered networks DUT‐8(Ni) and X‐pcu‐3‐Zn‐3 i , which contain the short pillar dabco and the rigid pillar 1,4‐bis(4‐pyridyl)benzene, respectively, offer much lower recyclability suggests that flexible dipyridyl‐type ligands may improve framework reversibility and recyclability.…”

Section: Methodsmentioning

confidence: 99%

Tuning the Gate‐Opening Pressure in a Switching pcu Coordination Network, X‐pcu‐5‐Zn, by Pillar‐Ligand Substitution

et al. 2019

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Coordination networks that reversibly switch between closed and open phases are of topical interest since their stepped isotherms can offer higher working capacities for gas‐storage applications than the related rigid porous coordination networks. To be of practical utility, the pressures at which switching occurs, the gate‐opening and gate‐closing pressures, must lie between the storage and delivery pressures. Here we study the effect of linker substitution to fine‐tune gate‐opening and gate‐closing pressure. Specifically, three variants of a previously reported pcu‐topology MOF, X‐pcu‐5‐Zn, have been prepared: X‐pcu‐6‐Zn, 6=1,2‐bis(4‐pyridyl)ethane (bpe), X‐pcu‐7‐Zn, 7=1,2‐bis(4‐pyridyl)acetylene (bpa), and X‐pcu‐8‐Zn, 8=4,4′‐azopyridine (apy). Each exhibited switching isotherms but at different gate‐opening pressures. The N2, CO2, C2H2, and C2H4 adsorption isotherms consistently indicated that the most flexible dipyridyl organic linker, 6, afforded lower gate‐opening and gate‐closing pressures. This simple design principle enables a rational control of the switching behavior in adsorbent materials.

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Tolerance of Flexible MOFs toward Repeated Adsorption Stress

Cited by 78 publications

References 35 publications

Collective Breathing in an Eightfold Interpenetrated Metal–Organic Framework: From Mechanistic Understanding towards Threshold Sensing Architectures

Collective Breathing in an Eightfold Interpenetrated Metal–Organic Framework: From Mechanistic Understanding towards Threshold Sensing Architectures

A Ligand Field Molecular Mechanics Study of CO₂‐Induced Breathing in the Metal–Organic Framework DUT‐8(Ni)

Tuning the Gate‐Opening Pressure in a Switching pcu Coordination Network, X‐pcu‐5‐Zn, by Pillar‐Ligand Substitution

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Tolerance of Flexible MOFs toward Repeated Adsorption Stress

Cited by 78 publications

References 35 publications

Collective Breathing in an Eightfold Interpenetrated Metal–Organic Framework: From Mechanistic Understanding towards Threshold Sensing Architectures

Collective Breathing in an Eightfold Interpenetrated Metal–Organic Framework: From Mechanistic Understanding towards Threshold Sensing Architectures

A Ligand Field Molecular Mechanics Study of CO2‐Induced Breathing in the Metal–Organic Framework DUT‐8(Ni)

Tuning the Gate‐Opening Pressure in a Switching pcu Coordination Network, X‐pcu‐5‐Zn, by Pillar‐Ligand Substitution

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A Ligand Field Molecular Mechanics Study of CO₂‐Induced Breathing in the Metal–Organic Framework DUT‐8(Ni)