Selective pore opening and gating of the pillared layer metal-organic framework DUT-8(Ni) upon liquid phase multi-component adsorption

Kavoosi, Negar; Savchenko, Tatiana; Senkovska, Irena; Maliuta, Mariia; Bon, Volodymyr; Eychmüller, Alexander; Kaskel, Stefan

doi:10.1016/j.micromeso.2018.05.024

Cited by 18 publications

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“…69 Higher interaction energies are expected for aprotic polar solvents (such as DMF), producing an opening of the framework independent on particle size for the DUT-8(Ni) system. 38 Resolvation of 1a_cp in liquid DMF, however, leads only to the opening of part of the sample, according to PXRD analysis ( Fig. S7, ESI †) suggesting crystal size dependent behaviour.…”

Section: Adsorption Behaviourmentioning

confidence: 99%

“…37 The nickel-based compound shows pronounced stimuli-induced "gating"-type exibility upon adsorption of gases and liquids. 38 In situ 129 Xe NMR and powder X-ray diffraction (PXRD) were used to elucidate the guest-framework interactions, framework dynamics and crystal structure of the closed pore phase, indicating an unprecedented unit cell volume change of 250% upon "gate opening". 39 Recent studies revealed that not only the chemical composition and average crystal structure, but also the real particle structure (size, morphology, defects) considerably affects the switchability, increasing the complexity of investigations.…”

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confidence: 99%

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Crystal size versus paddle wheel deformability: selective gated adsorption transitions of the switchable metal–organic frameworks DUT-8(Co) and DUT-8(Ni)

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Crystal size versus paddle wheel deformability: selective gated adsorption transitions of the switchable metal-organic frameworks and † Switchable pillared layer metal-organic frameworks M 2 (2,6-ndc) 2 (dabco) (DUT-8(M), M ¼ Ni, Co, 2,6-ndc ¼ 2,6naphthalenedicarboxylate, dabco ¼ 1,4-diazabicyclo-[2.2.2]octane, DUT -Dresden University of Technology) were synthesised in two different crystallite size regimes to produce particles up to 300 mm and smaller particles around 0.1 mm, respectively. The textural properties and adsorption-induced switchability of the materials, obtained from both syntheses, were studied by physisorption of N 2 at 77 K, CO 2 at 195 K and nbutane at 273 K, revealing pronounced differences in adsorption behavior for Ni and Co analogues. While the smaller nano-sized particles (50-200 nm) are rigid and show no gating transitions confirming the importance of crystallite size, the large particles show pronounced switchability with characteristic differences for the two metals resulting in distinct recognition effects for various gases and vapours. Adsorption of various vapours demonstrates consistently a higher energetic barrier for the "gate opening" of DUT-8(Co) in contrast to , as the "gate opening" pressure for Co based material is shifted to a higher value for adsorption of dichloromethane at 298 K. Evaluation of crystallographic data, obtained from single crystal and powder X-ray diffraction analysis, showed distinct geometric differences in the paddle wheel units of the respective MOFs.These differences are further disclosed by solid-state UV-vis, FT-IR and Raman spectroscopy. Magnetic properties of DUT-8(Co) and DUT-8(Ni) were investigated, indicating a high-spin state for both materials at room temperature. Density functional theory (DFT) simulations confirmed distinct energetic differences for Ni and Co analogues with a higher energetic penalty for the structural "gate opening" transformation for DUT-8(Co) compared to DUT-8(Ni) explaining the different flexibility behaviour of these isomorphous MOFs.underlying structural phase transitions are triggered by adsorption or desorption of guest molecules and generally characterised by an activation energy barrier, which causes hysteresis in physisorption experiments. Due to their switchable nature, so porous crystals are oen discussed as materials with huge application potential in gas storage, 11 separation processes, 12,13 sensor technology 14,15 and catalysis. 16 Despite rapidly growing research in the eld of exible MOFs, 1,17-21 the role of critical factors inuencing and controlling framework switchability are barely understood. 22 As MOFs are modular networks, the exibility of the linker but also the hinges of the metal node are key features that affect switchability. The importance of metal-node hinges and their energetics for framework switchability has been widely investigated for compounds such as M(bdp) (M ¼ Co, Fe, bdp ¼ 1,4-benzenedipyrazolate), 11,23,24 M(m-OH)(bdc) (MIL-53, M ¼ Cr, Al, Fe, bdc ¼ 1,4-benzenedicarboxylate)...

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Section: Adsorption Behaviourmentioning

confidence: 99%

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confidence: 99%

Crystal size versus paddle wheel deformability: selective gated adsorption transitions of the switchable metal–organic frameworks DUT-8(Co) and DUT-8(Ni)

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“…[14][15][16] Selective recognition of solvents with different polarity and chemical constitution was recently reported for DUT-8(Ni) with potential sensing applications. 17 However, selective adsorption and guest recognition in flexible MOFs are not fully understood yet. Further in-depth investigations are necessary.…”

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“…48,49 Former studies on DUT-8(Ni) showed distinct differences in the adsorption behaviour of aprotic polar and protic polar solvents like alcohols. 17 To investigate the influence of solvent molecules that can act as donor and acceptor (amphiprotic behaviour), we performed a series of experiments with various alcohols. Surprisingly, we could not find a direct correlation between the polarity of the alcohols and the chemical shift in the 13 C spectra (Fig.…”

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New insights into solvent-induced structural changes of ¹³C labelled metal–organic frameworks by solid state NMR

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Understanding MOF Flexibility: An Analysis Focused on Pillared Layer MOFs as a Model System

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Flexible porous frameworks are at the forefront of materials research. A unique feature is their ability to open and close their pores in an adaptive manner induced by chemical and physical stimuli. Such enzyme-like selective recognition offers a wide range of functions ranging from gas storage and separation to sensing, actuation, mechanical energy storage and catalysis. However, the factors affecting switchability are poorly understood. In particular, the role of building blocks, as well as secondary factors (crystal size, defects, cooperativity) and the role of host-guest interactions, profit from systematic investigations of an idealized model by advanced analytical techniques and simulations. The review describes an integrated approach targeting the deliberate design of pillared layer metal-organic frameworks as idealized model materials for the analysis of critical factors affecting framework dynamics and summarizes the resulting progress in their understanding and application.

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Selective pore opening and gating of the pillared layer metal-organic framework DUT-8(Ni) upon liquid phase multi-component adsorption

Cited by 18 publications

References 31 publications

Crystal size versus paddle wheel deformability: selective gated adsorption transitions of the switchable metal–organic frameworks DUT-8(Co) and DUT-8(Ni)

Crystal size versus paddle wheel deformability: selective gated adsorption transitions of the switchable metal–organic frameworks DUT-8(Co) and DUT-8(Ni)

New insights into solvent-induced structural changes of ¹³C labelled metal–organic frameworks by solid state NMR

Understanding MOF Flexibility: An Analysis Focused on Pillared Layer MOFs as a Model System

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Selective pore opening and gating of the pillared layer metal-organic framework DUT-8(Ni) upon liquid phase multi-component adsorption

Cited by 18 publications

References 31 publications

Crystal size versus paddle wheel deformability: selective gated adsorption transitions of the switchable metal–organic frameworks DUT-8(Co) and DUT-8(Ni)

Crystal size versus paddle wheel deformability: selective gated adsorption transitions of the switchable metal–organic frameworks DUT-8(Co) and DUT-8(Ni)

New insights into solvent-induced structural changes of 13C labelled metal–organic frameworks by solid state NMR

Understanding MOF Flexibility: An Analysis Focused on Pillared Layer MOFs as a Model System

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New insights into solvent-induced structural changes of ¹³C labelled metal–organic frameworks by solid state NMR