A Stimuli‐Responsive Zirconium Metal–Organic Framework Based on Supermolecular Design

Krause, Simon; Bon, Volodymyr; Stoeck, Ulrich; Senkovska, Irena; Többens, Daniel M.; Wallacher, Dirk; Kaskel, Stefan

doi:10.1002/anie.201702357

Cited by 81 publications

(74 citation statements)

References 59 publications

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“…Nitrogen isotherms at 77 K of both materials show a pronounced pressure reduction upon structural opening referred to by the authors as "negative gas pressure". Such artificial pressure reduction upon structural expansion is also observed in DUT-98 and a few other examples in the literature 23,[25][26][27] and is a clear indication for a metastable adsorption state as previously described by Kitagawa and co-workers 28 .…”

Section: Resultssupporting

confidence: 76%

“…The contraction mechanism in DUT-98(1) was previously shown to depend on pore shrinkage along a reorganization of water molecules within the structure close to the Zr-cluster 23 . The Diffuse Reflectance Fourier transform (DRIFT) spectroscopy shows typical vibrations corresponding to the linker and OH groups of the MOFs in all materials (Supplementary Figure 12).…”

Section: Resultsmentioning

confidence: 99%

“…The experiments were conducted under vacuum on supercritically activated DUT-98(2) in the temperature range of 30 -350 °C. These conditions are often used for thermal activation of MOFs and were previously applied on the analysis of DUT-98(1) 23 . In the range of 30 -75 °C no change in the PXRD patterns could be observed and the material could be heated and cold down within this rage without any indication of structural changes ( Figure 5).…”

Section: Resultsmentioning

confidence: 99%

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The impact of crystal size and temperature on the adsorption-induced flexibility of the Zr-based metal-organic framework DUT-98

Krause¹,

Bon²,

Du³

et al. 2019

Preprint

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In this contribution we analyse the influence of adsorption cycling, crystal size, and temperature on the switching behaviour of the flexible Zr-based metal-organic framework DUT-98. We observe a shift in the gate opening pressure upon cycling of adsorption experiments of micro meter-sized crystals and assign this to a fragmentation of the crystals. In a series of modulated syntheses we downsize the average crystal size of DUT-98 crystals from 120 µm to 50 nm and characterize the obtained solids by X-ray diffraction, infrared spectroscopy, as well as scanning and transmission electron microscopy. We analyse the adsorption behaviour by nitrogen and water adsorption at 77 K and 298 K, respectively and show that adsorption-induced flexibility is only observed for micro meter-sized crystals. Nanometer-sized crystals were found to exhibit reversible type I adsorption behaviour upon adsorption of nitrogen and exhibit a crystal-size dependent steep water uptake of up to 20 mmol g-1 at 0.5 p/p 0 with potential for water harvesting and heat pump applications. We furthermore investigate the temperature-induced structural transition by in situ PXRD. At temperatures beyond 110 °C the open pore state of nano meter-sized DUT-98 crystals are found to irreversibly transform in a closed pore state. The connection of crystal fragmentation upon adsorption cycling and the crystal size-dependence of the adsorption-induced flexibility is an important finding for evaluation of these materials in future adsorption-based applications. This work thus extends the limited amount of studies on crystal size effects in flexible MOFs and hopefully motivates further investigations into this field.

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Section: Resultssupporting

confidence: 76%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

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The impact of crystal size and temperature on the adsorption-induced flexibility of the Zr-based metal-organic framework DUT-98

Krause¹,

Bon²,

Du³

et al. 2019

Preprint

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“…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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“…The surface area agreement of zirconium‐based MOFs was analyzed by Wang et al where the members of the NU‐110x series that are based on carboxylate linkers were selected ( Figure ). Each acronym for this series of MOFs (together with other acronyms mentioned in this review) is described in Table 3 .…”

Section: The Agreement Between Different Types Of Bet Surface Areasmentioning

confidence: 99%

Evaluation of the BET Theory for the Characterization of Meso and Microporous MOFs

et al. 2018

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Surface area determination with the Brunauer–Emmett–Teller (BET) method is a widely used characterization technique for metal–organic frameworks (MOFs). Since these materials are highly porous, the use of the BET theory can be problematic. Several researchers have evaluated the BET method to gain insights into the usefulness of the obtained results and interestingly, their findings are not always consistent. In this review, the suitability of the BET method is discussed for MOFs that have a diverse range of pore widths below the diameters of N2 or Ar and above 20 Å. In addition, the surface area of MOFs that are obtained by implementing different approaches, such as grand canonical Monte Carlo simulations, calculations from the crystal structures or based on experimental N2, Ar, or CO2 adsorption isotherms, are compared and evaluated. Inconsistencies in the state‐of‐the‐art are also noted. Based on the current literature, an overview is provided of how the BET method can give useful estimations of the surface areas for the majority of MOFs, but there are some crucial and specific exceptions which are highlighted in this review.

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A Stimuli‐Responsive Zirconium Metal–Organic Framework Based on Supermolecular Design

Cited by 81 publications

References 59 publications

The impact of crystal size and temperature on the adsorption-induced flexibility of the Zr-based metal-organic framework DUT-98

The impact of crystal size and temperature on the adsorption-induced flexibility of the Zr-based metal-organic framework DUT-98

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

Evaluation of the BET Theory for the Characterization of Meso and Microporous MOFs

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