Flexible Metal-organic Frameworks Research Articles

Effect of Boron-Doping on Gate-Opening CO2 Adsorption in Zinc-Benzimidazolate Coordination Networks.

Flexible metal-organic frameworks (MOFs) have attracted much attention as selective gas adsorption and storage. This report describes boron doping in zeolitic imidazolate framework-7 (B-ZIF-7), which exhibits reversible phase transition during CO2 adsorption/desorption. We have successfully prepared B-ZIF-7 coordination networks using boron-bridged benzimidazolate (B(bim)4-) as organic ligands. Powder X-ray diffraction (PXRD) measurements and infrared spectroscopy revealed that B-ZIF-7 has a crystal structure similar to that of ZIF-7 while containing boron bridging in the coordination network. Since B-ZIF-7 forms a cationic coordination network, the guest anions are encapsulated within the pore. CO2 adsorption/desorption measurements at 300 K showed that B-ZIF-7(NO3), which contains nitrate ions (NO3-) as guest anions in its pores, exhibits a S-shaped CO2 adsorption/desorption isotherm, which is characteristic of gate-opening type MOFs. Compared with ZIF-7, B-ZIF-7(NO3) has superior CO2 adsorption capacity in the low-pressure and superior CO2 storage capacity. The CO2 adsorption and desorption behavior of B-ZIF-7(NO3) was analyzed by in situ temperature-controlled PXRD measurements and thermogravimetric analysis under a CO2 atmosphere, and a reversible phase transition was observed. We have also successfully prepared B-ZIF-7(Cl) and B-ZIF-7(OTf) (OTf = CF3SO3-) with different guest anions. The CO2 adsorption/desorption behaviors of B-ZIF-7(Cl) and B-ZIF-7(OTf) were significantly different from those of B-ZIF-7(NO3) and ZIF-7. B-ZIF-7(Cl) showed gate opening at a higher pressure than ZIF-7, and B-ZIF-7(OTf) did not show S-shaped CO2 adsorption isotherm and showed adsorption behavior in micropores. These results indicate that the CO2 adsorption behavior of B-ZIF-7 depends on the interaction between the guest anions and CO2 molecules or the cationic framework and the bulkiness of the guest anions. Boron doping in a coordination network with boron-bridged imidazolate ligands is a promising strategy to increase the gas adsorption capability of porous materials.

Controllable ion design in flexible metal organic framework film for performance regulation of electrochemical biosensing

The limitations of solvent residues, unmanageable film growth regions, and substandard performance impede the extensive utilization of metal-organic framework (MOF) films for biosensing devices. Here, we report a strategy for ion design in gas-phase synthesized flexible MOF porous film to attain universal regulation of biosensing performances. The key fabrication process involves atomic layer deposition of induced layer coupled with lithography-assisted patterning and area-selective gas-phase synthesis of MOF film within a chemical vapor deposition system. Sensing platforms are subsequently formed to achieve specific detection of H2O2, dopamine, and glucose molecules by respectively implanting Co, Fe, and Ni ions into the network structure of MOF films. Furthermore, we showcase a practical device constructed from Co ions-implanted ZIF-4 film to accomplish real-time surveillance of H2O2 concentration at mouse wound. This study specifically elucidates the electronic structure and coordination mode of ion design in MOF film, and the obtained knowledge aids in tuning the electrochemical property of MOF film for advantageous sensing devices.

Optimizing Trace Acetylene Removal from Acetylene/Ethylene Mixture in a Flexible Metal-Organic Framework by Crystal Downsizing.

Improving the gas separation performance of metal-organic frameworks (MOFs) by crystal downsizing is an important but often overlooked issue. Here, we report three different-sized flexible ZUL-520 MOFs (according to the crystal size from large to small, the three samples are, respectively, named ZUL-520-0, ZUL-520-1, and ZUL-520-2) with the same chemical structure for optimizing trace acetylene (C2H2) removal from acetylene/ethylene (C2H2/C2H4) mixture. The three differently sized activated ZUL-520 (denoted as ZUL-520a) exhibited almost identical C2H2 uptake of 4.8 mmol/g at 100 kPa, while the C2H2 uptake at 1 kPa increased with a downsizing crystal. The C2H2 uptake of activated ZUL-520-2 (denoted as ZUL-520-2a) at 1 kPa was ∼55% higher than that of activated ZUL-520-0 (denoted as ZUL-520-0a). The adsorption isotherms and adsorption kinetics validated that gas adsorptive separation is governed not only by adsorption thermodynamics but also by adsorption kinetics. In addition, all three different-sized ZUL-520a MOFs showed high C2H2/C2H4 selectivity. Grand canonical Monte Carlo (GCMC) simulations and dispersion-corrected density functional theory (DFT-D) computations illustrated a plausible mechanism of C2H2 adsorption in MOFs. Importantly, breakthrough experiments demonstrated that ZUL-520a can effectively separate the C2H2/C2H4 (1/99, v/v) mixture and the C2H4 productivity obtained by ZUL-520-2a was much higher than that by ZUL-520-0a. Our work may provide an easy but powerful strategy for upgrading the performance of gas adsorptive separation in MOFs.

Adsorption of Xenon, Krypton, and Their Mixture on the Flexible Metal–Organic Framework DUT-8(Ni)

Adsorption of Xenon, Krypton, and Their Mixture on the Flexible Metal–Organic Framework DUT-8(Ni)

Tunable Gas Admission via a "Molecular Trapdoor" Mechanism in a Flexible Cationic Metal-Organic Framework Featuring 1D Channels.

Achieving high gas selectivity is challenging when dealing with gas pairs of similar size and physiochemical properties. The "molecular trapdoor" mechanism discovered in zeolites holds promise for highly selective gas adsorption separation but faces limitations like constrained pore volume and slow adsorption kinetics. To address these challenges, for the first time, a flexible metal-organic framework (MOF) featuring 1D channels and functioning as a "molecular trapdoor" material is intoduced. Extra-framework anions act as "gate-keeping" groups at the narrowest points of channels, permitting gas admissions via gate opening induced by thermal/pressure stimuli and guest interactions. Different guest molecules induce varied energy barriers for anion movement, enabling gas separation based on distinct threshold temperatures for gas admission. The flexible framework of Pytpy MOFs, featuring swelling structure with rotatable pyridine rings, facilitates faster gas adsorption than zeolite. Analyzing anion properties of Pytpy MOFs reveals a guiding principle for selecting anions to tailor threshold gas admission. This study not only overcomes the kinetic limitations related to gas admission in the "molecular trapdoor" zeolites but also underscores the potential of developing MOFs as molecular trapdoor adsorbents, providing valuable insights for designing ionic MOFs tailored to diverse gas separation applications.

Selective Detection of Primary Aromatic Amines through Enhanced Luminescence of a 2D + 2D Inclined Polycatenated Microporous Nitro-Functionalized Metal-Organic Framework.

Detection and sensing of amines through enhanced fluorescence emission are always challenging in aqueous solution. The range of different Lewis basicities, shapes, and sizes as well as the different structural arrangements of amines is responsible for their less specificity in aqueous solution. Here, we have designed a highly fluorescent emissive 2D + 2D → 3D inclined polycatenated NO2-functionalized flexible metal-organic framework (MOF) for selective segregation of electron-rich aromatic primary amines from electron-deficient amines in aqueous solution, showing different emission behaviors. The inclined polycatenated 2D + 2D → 3D MOF having an asymmetric unit {[Cd(dim)(2-nta)(H2O)](H2O)(MeOH)}n (1) has been synthesized by a slow diffusion process and characterized thoroughly by single-crystal and powder X-ray diffraction (PXRD) as well as other physicochemical methods. The desolvated species of 1 (Ref. MOF) is found to be stable and has been characterized by PXRD and adsorption study. The fluorescence profile of the Ref. MOF shows selective enhancement in the presence of electron-rich primary aromatic amines, while the same shows quenching for electron-deficient amines in aqueous solution. The Ref. MOF reported here consists of flexible space between two 2D layers that is responsible for different orientations for different analyte primary aromatic amines (PAAs) with different sizes. The above findings are also supported by time-resolved fluorescence spectroscopy. The respective fluorescence enhancement and quenching have been explained by the interaction between the CB of the host MOF and LUMO of guest amines. Therefore, this work presents an operable method for the sensing of PAAs using a single compound, which is a polycatenated MOF.

Deep Learning Enabled SERS Identification of Gaseous Molecules on Flexible Plasmonic MOF Nanowire Films.

Through the capture of a target molecule at the metal surface with a highly confined electromagnetic field induced by surface plasmon, surface enhanced Raman spectroscopy (SERS) emerges as a spectral analysis technology with high sensitivity. However, accurate SERS identification of a gaseous molecule with low density and high velocity is still a challenge due to its difficulty in capture. In this work, a flexible paper-based plasmonic metal-organic framework (MOF) film consisting of Ag nanowires@ZIF-8 (AgNWs@ZIF-8) is fabricated for SERS detection of gaseous molecules. Benefiting from its micronanopores generated by the nanowire network and ZIF-8 shell, the effective capture of the gaseous molecule is achieved, and its SERS spectrum is obtained in this paper-based flexible plasmonic MOF nanowire film. With optimal structure parameters, spectra of gaseous 4-aminothiophenol, 4-mercaptophenol, and dithiohydroquinone demonstrate that this film has good SERS performance, which could maintain obvious Raman signals within 30 days during reproducible detection. To realize SERS identification of gaseous molecules, deep learning is performed based on the SERS spectra of the mixed gaseous analyte obtained in this flexible porous film. The results point out that an artificial neural network algorithm could identify gaseous aldehydes (gaseous biomarker of colorectal cancer) in simulated exhaled breath with high accuracy at 93.7%. The integration of the flexible paper-based film sensors with deep learning offers a promising new approach for noninvasive colorectal cancer screening. Our work explores SERS applications in gaseous analyte detection and has broad potential in clinical medicine, food safety, environmental monitoring, etc.

MIL-53(Fe) anode for lithium-ion batteries with the capacity self-activation effect based on electrochemically induced crystalline-to-amorphization transformation

The relationship between structural changes and electrochemical properties of flexible metal-organic framework materials is a striking phenomenon. We synthesized a highly ordered flexible metal-organic framework called MIL-53(Fe) as an anode for lithium-ion batteries. MIL-53(Fe) 's cyclic performance exhibits capacity self-activation traits. At 100 mA g−1 current density, the specific discharge capacity of 100 cycles is 931.23 mAh g−1, the coulomb efficiency is 98.53%, and the capacity retention rate is 92.60%. The evolution of MIL-53(Fe) throughout the cycle was observed using X-ray diffraction, Raman spectroscopy, and high-resolution transmission electron microscopy. It was discovered that the structure of MIL-53(Fe) experienced an electrochemically induced transition from a crystalline state to an amorphous state. After amorphous conversion, the electrochemical transfer impedance of the material is reduced from 177.2 Ω to 40.6 Ω, the diffusion coefficient of lithium-ion is increased from 3.32 × 10−14 cm2/s to 1.10 × 10−13 cm2/s, and the mass transfer capacity is improved. The results show that MIL-53(Fe) has unique electrochemical properties, and the feasibility of amorphous transition as a mechanism to enhance the electrochemical properties is found.

Enhancing contaminant rejection efficiency with ZIF-8 molecular sieving in sustainable mixed matrix membranes

Compared to pure polymer membranes and inorganic membranes, mixed matrix membranes (MMMs) loaded with metal–organic frameworks (MOFs) exhibit higher permeability and selectivity. Zeolitic imidazolate framework (ZIF) is widely regarded as the most promising candidate for separation membrane materials due to its precise molecular sieving properties. However, there is an urgent need for scalable fabrication methods to produce flexible and sustainable MOF MMMs, which is largely unmet. Here, we report a non-solvent induced phase separation-spin coating (NIPS-SC) strategy for the preparation of highly permeable MOF MMMs. A porous support layer is formed by non-solvent induced phase separation of polyvinylidene fluoride (PVDF) and polyvinylpyrrolidone (PVP). Chitosan (CS), polyvinyl alcohol (PVA), and ZIF-8 are then coated on the PVDF support layer to synthesize the symbiotic and continuous MMM membrane. The synthesized membrane shows excellent separation performance for organic dye and heavy metal ions, as well as significant stability. The water permeate flux of the membrane is 342 L m–2 h−1 bar−1. The micron-scale in the support layer facilitates rapid water permeation, while the porous ZIF-8 provides enhanced solute rejection selectivity. This strategy paves the way for the development of high-performance membranes for water purification.

Chemoselectivity Inversion of Responsive Metal-Organic Frameworks by Particle Size Tuning in the Micrometer Regime.

Gated adsorption is one of the unique physical properties of flexible metal-organic frameworks with high application potential in selective adsorption and sensing of molecules. Despite recent studies that have provided some guidelines in understanding and designing structural flexibility for controlling gate opening by chemical modification of the secondary building units, currently, there is no established strategy to design a flexible MOF showing selective gated adsorption for a specific guest molecule. In a present contribution it is demonstrated for the first time, that the selectivity in the gate opening of a particular compound can be tuned, changed, and even reversed using particle size engineering DUT-8(Zn) ([Zn2(2,6-ndc)2(dabco)]n, 2,6-ndc=2,6-naphthalenedicarboxylate, dabco=1,4-diazabicyclo-[2.2.2]-octane, DUT = Dresden University of Technology) experiences phase transition from open (op) to closed (cp) pore phase upon removal of solvent from the pores. Microcrystals show selective reopening in the presence of dichloromethane (DCM) over alcohols. Crystal downsizing to micron size unexpectedly reverses the gate opening selectivity, causing DUT-8(Zn) to open its nanosized pores for alcohols but suppressing the responsivity toward DCM.

Elucidating the particle size-dependent guest-induced structural transition of flexible metal–organic frameworks by exploring cooperative nature

Flexible metal–organic frameworks (MOFs) show S-shaped adsorption isotherms due to their structural transition. This behavior changes depending on their particle size. This paper elucidates the size effect using a multi-scale simulation model.

Guest-selective shape-memory effect in a switchable metal-organic framework DUT-8(Zn).

Crystal size engineering allows tailoring of flexible metal-organic frameworks (MOFs) to achieve new properties. The gating type flexibility of the DUT-8(Zn) ([Zn2(2,6-ndc)2(dabco)]n, 2,6-ndc = 2,6-naphthalene dicarboxylate, dabco = 1,4-diazabicyclo-[2.2.2]-octane) compound is known to be extremely particle size sensitive. Here, the physisorption of ethanol vapor gives rise to so-called shape-memory effect, leading to rigidification and flexibility suppression. According to powder X-ray diffraction and nitrogen physisorption experiments, the open pore phase is retained selectively after desorption of alcohols, which could be attributed to the nano-structuring and surface deformation of the crystals as a result of exposure to alcohols.

Nitrogen-enriched flexible metal-organic framework for CO2 adsorption.

A novel MOF named [Zn2(L)(DMF)] was synthesized using solvothermal methods from the reaction of the new linker (4,4',4''-(4,4',4''-(benzene-1,3,5-triyltris(methylene))tris(3,5-dimethyl-1H-pyrazole-4,1-diyl))tribenzoic acid) and Zn(NO3)2·6H2O. This new MOF was characterized by means of different techniques: powder X-ray diffraction, N2 adsorption and desorption isotherms, thermogravimetric analysis, and scanning electron microscopy. Furthermore, suitable crystals were obtained, which allowed us to perform the X-Ray structure determination of this MOF. The capability of these new MOF to adsorb CO2 at different temperatures was measured and its isosteric enthalpy of adsorption was calculated. The novel MOF shows an uncommon node composed of a Zn3(-COO)6(DMF)2, and the asymmetric unit contains one crystallographically independent linker, one DMF molecule, and two Zn atoms. The [Zn2(L)(DMF)] MOF is a microporous material with high crystallinity and stability up to 250 °C. The multiple nitrogenated pyrazole linkers in its framework enhance its CO2 adsorption capabilities. This material exhibits a low CO2 isosteric enthalpy of adsorption (Hads), comparable to previously reported values for similar nitrogenated materials. All the observed CO2 adsorption capacities were further supported by DFT calculations.

Vertical MOF film supported on an organic–inorganic mixed substrate for complex wastewater purification

Flexible metal–organic framework (MOF) films are greatly desired for the separation of hazardous molecules and ions from wastewater. The current MOF films are usually horizontally deposited on the substrates, and thus restricted by brittleness, low exposure of surface area, as well as poor separation functions. Here, an organic–inorganic mixed substrate is firstly fabricated by growing hydroxyapatite (HA) nanowire arrays on the cellulose fiber (CF). Subsequently, MIL-100(Fe) nanocrystals are assembled on the surfaces of HA nanowire arrays through a layer-by-layer manner, leading to a unique vertical MOF film. The resulting vertical MOF films show competitive advantages over the horizontal counterparts: (i) they show excellent flexibility and they are tolerant to serious physical damage; (ii) they have multiple separation functions including ion exchange of HA, excellent adsorption of MOFs, and strong electrostatic interaction of CF; and (iii) the agglomeration of MIL-100(Fe) nanocrystals is effectively suppressed. Therefore, the average roughness, specific surface area, and average pore size of films are optimized. As a result, the vertical MOF films show universal separation of positively/negatively-charged dyes and Pb2+ ion, with high removal rates of > 94 %. More appealing, the mixed pollutants in the complex wastewater can be one-step separated through the vertical MOF films, with high removal rates of > 96 %.

A Critical Assessment on Calculating Vibrational Spectra in Nanostructured Materials.

Vibrational spectroscopy is an omnipresent spectroscopic technique to characterize functional nanostructured materials such as zeolites, metal-organic frameworks (MOFs), and metal-halide perovskites (MHPs). The resulting experimental spectra are usually complex, with both low-frequency framework modes and high-frequency functional group vibrations. Therefore, theoretically calculated spectra are often an essential element to elucidate the vibrational fingerprint. In principle, there are two possible approaches to calculate vibrational spectra: (i) a static approach that approximates the potential energy surface (PES) as a set of independent harmonic oscillators and (ii) a dynamic approach that explicitly samples the PES around equilibrium by integrating Newton's equations of motions. The dynamic approach considers anharmonic and temperature effects and provides a more genuine representation of materials at true operating conditions; however, such simulations come at a substantially increased computational cost. This is certainly true when forces and energy evaluations are performed at the quantum mechanical level. Molecular dynamics (MD) techniques have become more established within the field of computational chemistry. Yet, for the prediction of infrared (IR) and Raman spectra of nanostructured materials, their usage has been less explored and remain restricted to some isolated successes. Therefore, it is currently not a priori clear which methodology should be used to accurately predict vibrational spectra for a given system. A comprehensive comparative study between various theoretical methods and experimental spectra for a broad set of nanostructured materials is so far lacking. To fill this gap, we herein present a concise overview on which methodology is suited to accurately predict vibrational spectra for a broad range of nanostructured materials and formulate a series of theoretical guidelines to this purpose. To this end, four different case studies are considered, each treating a particular material aspect, namely breathing in flexible MOFs, characterization of defects in the rigid MOF UiO-66, anharmonic vibrations in the metal-halide perovskite CsPbBr3, and guest adsorption on the pores of the zeolite H-SSZ-13. For all four materials, in their guest- and defect-free state and at sufficiently low temperatures, both the static and dynamic approach yield qualitatively similar spectra in agreement with experimental results. When the temperature is increased, the harmonic approximation starts to fail for CsPbBr3 due to the presence of anharmonic phonon modes. Also, the spectroscopic fingerprints of defects and guest species are insufficiently well predicted by a simple harmonic model. Both phenomena flatten the potential energy surface (PES), which facilitates the transitions between metastable states, necessitating dynamic sampling. On the basis of the four case studies treated in this Review, we can propose the following theoretical guidelines to simulate accurate vibrational spectra of functional solid-state materials: (i) For nanostructured crystalline framework materials at low temperature, insights into the lattice dynamics can be obtained using a static approach relying on a few points on the PES and an independent set of harmonic oscillators. (ii) When the material is evaluated at higher temperatures or when additional complexity enters the system, e.g., strong anharmonicity, defects, or guest species, the harmonic regime breaks down and dynamic sampling is required for a correct prediction of the phonon spectrum. These guidelines and their illustrations for prototype material classes can help experimental and theoretical researchers to enhance the knowledge obtained from a lattice dynamics study.

Flattening of a Bent Sulfonated MOF Linker: Impact on Structures, Flexibility, Gas Adsorption, CO2/N2 Selectivity, and Proton Conduction.

Rational design of organic building blocks provides opportunities to control and tune various physicochemical properties of metal-organic frameworks (MOFs), including gas handling, proton conduction, and structural flexibility, the latter of which is responsible for new adsorption phenomena and often superior properties compared to rigid porous materials. In this work, we report synthesis, crystal structures, gas adsorption, and proton conduction for a flexible two-dimensional cadmium-based MOF (JUK-13-SO3H-SO2) containing a new sulfonated 4,4'-oxybis(benzoate) linker with a blocking SO2 bridge. This two-dimensional (2D) MOF is compared in detail with a previously reported three-dimensional Cd-MOF (JUK-13-SO3H), based on analogous, but nonflat, SO2-free sulfonated dicarboxylate. The comprehensive structure-property relationships and the detailed comparisons with insights into the networks flexibility are supported by five guest-dependent structures determined by single-crystal X-ray diffraction (XRD), and corroborated by spectroscopy (IR, 1H NMR), powder XRD, and elemental/thermogravimetric analyses, as well as by volumetric adsorption measurements (for N2, CO2, H2O), ideal adsorbed solution theory (IAST), density-functional theory (DFT+D) quantum chemical and grand-canonical Monte Carlo (GCMC) calculations, and electrochemical impedance spectroscopy (EIS) studies. Whereas both dynamic MOFs show moderate proton conductivity values, they exhibit excellent CO2/N2 selectivity related to the capture of CO2 from flue gases (IAST coefficients for 15:85 mixtures are equal to ca. 250 at 1 bar and 298 K). The presence of terminal sulfonate groups in both MOFs, introduced using a unique prechlorosulfonation strategy, is responsible for their hydrophilicity and water-assisted proton transport ability. The dynamic nature of the MOFs results in the appearance of breathing-type adsorption isotherms that exhibit large hysteresis loops (for CO2 and H2O) attributed to strong host-guest interactions. Theoretical modeling provides information about the adsorption mechanism and supports interpretation of experimental CO2 adsorption isotherms.

Highly effective quantum sieving of hydrogen isotopes on flexible metal-organic frameworks with mobile ligands

The separation of hydrogen isotopes is crucial in nuclear energy and biomedicine, but current techniques have limited separation coefficients. Utilizing flexible metal-organic frameworks (MOFs) with quantum sieving capabilities offers a promising solution. However, achieving high hydrogen isotope adsorption capacity while maintaining a high separation factor remains a challenge. This study presents a novel approach for the quantum sieving of hydrogen isotopes using MOFs with mobile ligands. The stable crystal structure of the microporous MOFs enables large hydrogen isotope adsorption capacity. The presence of mobile ligands acts as the gate in the dynamic adsorption and separation process, enhancing the performance of hydrogen isotope separation. The smaller quantum radius and larger molecular weight of deuterium facilitate its easier entry into the micropores, resulting in a maximum selectivity for D2 over H2 of 36.7 and a D2 uptake of 17.3 mmol g−1. Furthermore, the kinetic quantum sieving of hydrogen isotopes necessitates MOFs with mobile ligands that maintain their flexibility from 20 K to 70 K, as demonstrated by ultralow-frequency Raman spectra.

Oriented Self-assembly of Flexible MOFs Nanocrystals into Anisotropic Superstructures with Homogeneous Hydrogels Behaviors.

Building of metal-organic frameworks (MOFs) homogeneous hydrogels made by spontaneous crystallization remains a significant challenge. Inspired by anisotropically structured materials in nature, an oriented super-assembly strategy to construct micro-scale MOFs superstructure is reported, in which the strong intermolecular interactions between zirconium-oxygen (Zr─O) cluster and glutamic acid are utilized to drive the self-assembly of flexible nanoribbons into pumpkin-like microspheres. The confined effect between water-flexible building blocks and crosslinked hydrogen networks of superstructures achieved a mismatch transformation of MOFs powders into homogeneous hydrogels. Importantly, the elastic and rigid properties of hydrogels can be simply controlled by precise modulation of coordination and self-assembly for anisotropic superstructure. Experimental results and theoretical calculations demonstrates that MOFs anisotropic superstructure exhibits dynamic double networks with a superior water harvesting capacity (119.73gg-1) accompanied with heavy metal removal (1331.67mgg-1) and strong mechanical strength (Young's modulus of 0.3GPa). The study highlights the unique possibility of tailoring MOFs superstructure with homogeneous hydrogel behavior for application in diverse fields.

Facile shaping of flexible MIL-53(Al) for effective separation of propylene over propane

A facile granulation approach using polyvinyl butyral (PVB) as a polymer binder was developed to control the textural properties of the flexible metal–organic framework MIL-53(Al). The large pore (LP) structure of MIL-53(Al) contracted after granulation due to a strong interaction between MOF and polymer binder. This contraction enhances propylene's selectivity over propane at saturation pressure (region II), as confirmed by single-component adsorption isotherms. The adsorption kinetics showed faster adsorption of C3H6 compared to C3H8 over time in the case of the granules, while no difference was observed for the powder sample. Breakthrough experiments successfully separated C3H6 over C3H8 using MIL-53(Al)-B10% granules, whereas the pristine MIL-53(Al) powder did not separate the C3H8-C3H6 gas mixture. The breakthrough finding reaffirms that the observed gate-opening effect in MIL-53(Al) within pressure region I is ineffective for separating a mixed gas system containing propane and propylene. The constrained pores of the shaped granules could facilitate strong π-π stacking interactions with C3H6 and decrease the diffusion rate for C3H8 molecules. These findings indicate that the simple granulation approach can modulate the textural properties of flexible MIL-53(Al) and improve its selectivity for C3H6/C3H8 separation resulting from increased MOF-propylene affinity and kinetic factors.

Generalised analytical method unravels framework-dependent kinetics of adsorption-induced structural transition in flexible metal–organic frameworks

Flexible metal–organic frameworks (MOFs) exhibiting adsorption-induced structural transition can revolutionise adsorption separation processes, including CO2 separation, which has become increasingly important in recent years. However, the kinetics of this structural transition remains poorly understood despite being crucial to process design. Here, the CO2-induced gate opening of ELM-11 ([Cu(BF4)2(4,4’-bipyridine)2]n) is investigated by time-resolved in situ X-ray powder diffraction, and a theoretical kinetic model of this process is developed to gain atomistic insight into the transition dynamics. The thus-developed model consists of the differential pressure from the gate opening (indicating the ease of structural transition) and reaction model terms (indicating the transition propagation within the crystal). The reaction model of ELM-11 is an autocatalytic reaction with two pathways for CO2 penetration of the framework. Moreover, gas adsorption analyses of two other flexible MOFs with different flexibilities indicate that the kinetics of the adsorption-induced structural transition is highly dependent on framework structure.