Observation of a Reversible Order-Order Transition in a Metal-Organic Framework - Ionic Liquid Nanocomposite Phase-Change Material.

Metal-organic framework (MOF) composite materials containing ionic liquids (ILs) have been proposed for a range of potential applications, including gas separation, ion conduction, and hybrid glass formation. Here, an order transition in an IL@MOF composite is discovered using CuBTC (copper benzene-1,3,5-tricarboxylate) and [EMIM][TFSI] (1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide). This transition - absent for the bare MOF or IL - provides an extended super-cooling range and latent heat at a capacity similar to that of soft paraffins, in the temperature range of ≈220 °C. Structural analysis and in situ monitoring indicate an electrostatic interaction between the IL molecules and the Cu paddle-wheels, leading to a decrease in pore symmetry at low temperature. These interactions are reversibly released above the transition temperature, which reflects in a volume expansion of the MOF-IL composite.

Micro-optical elements from optical-quality ZIF-62 hybrid glasses by hot imprinting.

Hybrid glasses derived from meltable metal-organic frameworks (MOFs) promise to combine the intriguing properties of MOFs with the universal processing ability of glasses. However, the shaping of hybrid glasses in their liquid state - in analogy to conventional glass processing - has been elusive thus far. Here, we present optical-quality glasses derived from the zeolitic imidazole framework ZIF-62 in the form of cm-scale objects. These allow for in-depth studies of optical transparency and refraction across the ultraviolet to near-infrared spectral range. Fundamental viscosity data are reported using a ball penetration technique, and subsequently employed to demonstrate the fabrication of micro-optical devices by thermal imprinting. Using 3D-printed fused silica templates, we show that concave as well as convex lens structures can be obtained at high precision by remelting the glass without trading-off on material quality. This enables multifunctional micro-optical devices combining the gas uptake and permeation ability of MOFs with the optical functionality of glass. As an example, we demonstrate the reversible change of optical refraction upon the incorporation of volatile guest molecules.

Precise control over gas-transporting channels in zeolitic imidazolate framework glasses.

Porous metal-organic frameworks have emerged to resolve important challenges of our modern society, such as CO2 sequestration. Zeolitic imidazolate frameworks (ZIFs) can undergo a glass transition to form ZIF glasses; they combine the liquid handling of classical glasses with the tremendous potential for gas separation applications of ZIFs. Using millimetre-sized ZIF-62 single crystals and centimetre-sized ZIF-62 glass, we demonstrate the scalability and processability of our materials. Further, following the evolution of gas penetration into ZIF crystals and ZIF glasses by infrared microimaging techniques, we determine the diffusion coefficients and changes to the pore architecture on the ångström scale. The evolution of the material on melting and processing is observed in situ on different length scales by using a microscope-coupled heating stage and analysed microstructurally by transmission electron microscopy. Pore collapse during glass processing is further tracked by changes in the volume and density of the glasses. Mass spectrometry was utilized to investigate the crystal-to-glass transition and thermal-processing ability. The controllable tuning of the pore diameter in ZIF glass may enable liquid-processable ZIF glass membranes for challenging gas separations.

Pore-in-Pore Engineering in a Covalent Organic Framework Membrane for Gas Separation.

Covalent organic framework (COF) membranes have emerged as a promising candidate for energy-efficient separations, but the angstrom-precision control of the channel size in the subnanometer region remains a challenge that has so far restricted their potential for gas separation. Herein, we report an ultramicropore-in-nanopore concept of engineering matreshka-like pore-channels inside a COF membrane. In this concept, α-cyclodextrin (α-CD) is in situ encapsulated during the interfacial polymerization which presumably results in a linear assembly (LA) of α-CDs in the 1D nanochannels of COF. The LA-α-CD-in-TpPa-1 membrane shows a high H2 permeance (∼3000 GPU) together with an enhanced selectivity (>30) of H2 over CO2 and CH4 due to the formation of fast and selective H2-transport pathways. The overall performance for H2/CO2 and H2/CH4 separation transcends the Robeson upper bounds and ranks among the most powerful H2-selective membranes. The versatility of this strategy is demonstrated by synthesizing different types of LA-α-CD-in-COF membranes.

Fast Dynamic Synthesis of MIL-68(In) Thin Films in High Optical Quality for Optical Cavity Sensing.

Fabrication of metal-organic framework (MOF) thin films rigidly anchored on suitable substrates is a crucial prerequisite for the integration of these porous hybrid materials into electronic and optical devices. Thus, far, the structural variety for MOF thin films available through layer-by-layer deposition was limited, as the preparation of those surface-anchored metal-organic frameworks (SURMOFs) has several requirements: mild conditions, low temperatures, day-long reaction times, and nonaggressive solvents. We herein present a fast method for the preparation of the MIL SURMOF on Au-surfaces under rather harsh conditions: Using a dynamic layer-by-layer synthesis for MIL-68(In), thin films of adjustable thickness between 50 and 2000 nm could be deposited within only 60 min. The MIL-68(In) thin film growth was monitored in situ using a quartz crystal microbalance. In-plane X-ray diffraction revealed oriented MIL-68(In) growth with the pore-channels of this interesting MOF aligned parallel to the support. Scanning electron microscopy data demonstrated an extraordinarily low roughness of the MIL-68(In) thin films. Mechanical properties and lateral homogeneity of the layer were probed through nanoindentation. These thin films showed extremely high optical quality. By applying a poly(methyl methacrylate) layer and further depositing an Au-mirror to the top, a MOF optical cavity was fabricated that can be used as a Fabry-Perot interferometer. The MIL-68(In)-based cavity showed a series of sharp resonances in the ultraviolet-visible regime. Changes in the refractive index of MIL-68(In) caused by exposure to volatile compounds led to pronounced position shifts of the resonances. Thus, these cavities are well suited to be used as optical read-out sensors.

Aerogelation of Polymer-Coated Photoluminescent, Plasmonic, and Magnetic Nanoparticles for Biosensing Applications.

Macroscopic materials with nanoscopic properties have recently been synthesized by self-assembling defined nanoparticles to form self-supported networks, so-called aerogels. Motivated by the promising properties of this class of materials, the search for versatile routes toward the controlled assembly of presynthesized nanoparticles into such ultralight macroscopic materials has become a great interest. Overcoating procedures of colloidal nanoparticles with polymers offer versatile means to produce aerogels from nanoparticles, regardless of their size, shape, or properties while retaining their original characteristics. Herein, we report on the surface modification and assembly of various building blocks: photoluminescent nanorods, magnetic nanospheres, and plasmonic nanocubes with particle sizes between 5 and 40 nm. The polymer employed for the coating was poly(isobutylene-alt-maleic anhydride) modified with 1-dodecylamine side chains. The amphiphilic character of the polymer facilitates the stability of the nanocrystals in aqueous media. Hydrogels are prepared via triggering the colloidally stable solutions, with aqueous cations acting as linkers between the functional groups of the polymer shell. Upon supercritical drying, the hydrogels are successfully converted into macroscopic aerogels with highly porous, open structure. Due to the noninvasive preparation method, the nanoscopic properties of the building blocks are retained in the monolithic aerogels, leading to the powerful transfer of these properties to the macroscale. The open pore system, the universality of the polymer-coating strategy, and the large accessibility of the network make these gel structures promising biosensing platforms. Functionalizing the polymer shell with biomolecules opens up the possibility to utilize the nanoscopic properties of the building blocks in fluorescent probing, magnetoresistive sensing, and plasmonic-driven thermal sensing.

Current Trends in Metal-Organic and Covalent Organic Framework Membrane Materials.

Metal-organic frameworks (MOFs) and covalent organic frameworks (COFs) have been thoroughly investigated with regards to applications in gas separation membranes in the past years. More recently, new preparation methods for MOFs and COFs as particles and thin-film membranes, as well as for mixed-matrix membranes (MMMs) have been developed. We will highlight novel processes and highly functional materials: Zeolitic imidazolate frameworks (ZIFs) can be transformed into glasses and we will give an insight into their use for membranes. In addition, liquids with permanent porosity offer solution processability for the manufacture of extremely potent MMMs. Also, MOF materials influenced by external stimuli give new directions for the enhancement of performance by in situ techniques. Presently, COFs with their large pores are useful in quantum sieving applications, and by exploiting the stacking behavior also molecular sieving COF membranes are possible. Similarly, porous polymers can be constructed using MOF templates, which then find use in gas separation membranes.

Introducing electrical conductivity to metal-organic framework thin films by templated polymerization of methyl propiolate.

We herein present a case study on the templated, Pd-catalyzed polymerization reaction of methyl propiolate in the confined pore space of three different surface anchored metal-organic framework (SURMOF) systems in order to introduce electrical conductivity to MOF thin films and provide predictions for potential device integrations. To gain comprehensive insight into the influence of the template on polymerization, we chose Cu(bpdc), Cu2(bdc)2(dabco) and HKUST-1 because of their different types of pore channels, 1D, quasi-1D and 3D, and their free pore volumes. Well-defined MOF thin films were prepared using layer-by-layer deposition, which allows for the application of several characterization techniques not applicable for conventional powder MOFs. With SEM, AFM, XRD, MALDI-ToF/MS, ToF-SIMS and QCM, we were able to investigate the behaviour of the polymer formation. For lower dimensional pore channels, we find a depot-like release of monomeric units leading to top-layer formation determined by desorption kinetics, whereas for the 3D channels, quick release of an excess amount of monomers was observed and polymerization proceeds perfectly. Despite polymerization issues, control over the maximum chain lengths and the molecular weight distribution was achieved depending on the dimensionality of the pore systems. For the HKUST-1 system, polymerization was optimized and we were able to measure the electrical conductivity introduced by the conjugated polymer inside the channels.

Solution processable metal-organic frameworks for mixed matrix membranes using porous liquids.

The combination of well-defined molecular cavities and chemical functionality makes crystalline porous solids attractive for a great number of technological applications, from catalysis to gas separation. However, in contrast to other widely applied synthetic solids such as polymers, the lack of processability of crystalline extended solids hampers their application. In this work, we demonstrate that metal-organic frameworks, a type of highly crystalline porous solid, can be made solution processable via outer surface functionalization using N-heterocyclic carbene ligands. Selective outer surface functionalization of relatively large nanoparticles (250 nm) of the well-known zeolitic imidazolate framework ZIF-67 allows for the stabilization of processable dispersions exhibiting permanent porosity. The resulting type III porous liquids can either be directly deployed as liquid adsorbents or be co-processed with state-of-the-art polymers to yield highly loaded mixed matrix membranes with excellent mechanical properties and an outstanding performance in the challenging separation of propylene from propane. We anticipate that this approach can be extended to other metal-organic frameworks and other applications.

Studying ZIF-8 SURMOF Thin Films with a Langatate Crystal Microbalance: Single-Component Gas Adsorption Isotherms Measured at Elevated Temperatures and Pressures.

Characterizing the adsorption behavior of thin films at technical operation ranges is highly relevant in order to obtain appropriate experimental parameters, as well as to evaluate their possible integration in multiple applications. Nonetheless, gathering such experimental data is not a trivial task. In the case of metal-organic framework thin films, a particular interesting class of highly porous coatings, determination of adsorption isotherms at elevated temperatures and pressures is not commonly reported. Using a custom-designed langatate crystal microbalance following the principle for piezoelectric microbalances, but under harsher conditions, allowed us to present adsorption equilibrium measurements on a zeolitic imidazolate framework-8 (ZIF-8) surface-mounted metal-organic framework (SURMOF) thin film at temperatures between 35 and 100 °C and at a pressure range up to 10 bars. The layer-by-layer liquid-phase epitaxy approach was used to deposit ZIF-8 SURMOF thin films on langatate crystals. X-ray diffraction, infrared reflection absorption spectroscopy, and scanning electron microscopy combined with energy dispersive X-ray mapping were used to gather deeper information on the ZIF-8 thin film growth. Single-component isotherms were collected for different gases of practical interest, that is, CO2, C2H6, C2H4, C3H8, and C3H6. The measurements were obtained at 35, 50, 75, and 100 °C at a gauge pressure range up to 10 bars. The collected data showed a clear preferential adsorption of ethane over ethylene, whereas only a slight difference was found between propane and propylene. Additionally, the experimental data allowed for the determination of adsorption equilibrium constants and saturation loadings of the ZIF-8 material as a thin SURMOF film, which is of great importance for its integration in multiple applications, such as sensor devices or in membrane-based separation.

Covalent Organic Framework-Covalent Organic Framework Bilayer Membranes for Highly Selective Gas Separation.

Covalent organic frameworks (COFs) have been proposed as alternative candidates for molecular sieving membranes due to their chemical stability. However, developing COF membranes with narrowed apertures close to the size of common gas molecules is a crucial task for selective gas separation. Herein, we demonstrate a new type of a two-dimensional layered-stacking COF-COF composite membrane in bilayer geometry synthesized on a porous support by successively regulating the growth of imine-based COF-LZU1 and azine-based ACOF-1 layers via a temperature-swing solvothermal approach. The resultant COF-LZU1-ACOF-1 bilayer membrane has much higher separation selectivity for H2/CO2, H2/N2, and H2/CH4 gas mixtures than the individual COF-LZU1 and ACOF-1 membranes due to the formation of interlaced pore networks, and the overall performance surpasses the Robeson upper bounds. The COF-LZU1-ACOF-1 bilayer membrane also shows high thermal and long-time stabilities.

The Interaction of Guest Molecules with Co-MOF-74: A Vis/NIR and Raman Approach.

Co-MOF-74 rod like crystals with a length of several hundred micrometers are synthesized by a solvothermal procedure and their interaction with different gases is evaluated for selective gas sensing. We show strongly anisotropic absorption behavior of the Co-MOF-74 crystals when illuminated with polarized light. The interactions of guests (CO2 , propane, propene, Ar, MeOH, H2 O) with Co-MOF-74, is studied by various spectroscopic techniques. Vis/NIR shows peak shifts of Co-MOF-74 depending on the interaction with the guest. In the visible and the NIR the maximum absorbance is shifted selectively corresponding to the intensity of the CoII -guest interaction. Even propene and propane could be distinguished at room temperature by their different interactions with Co-MOF-74. Raman spectroscopy was used to detect a modified vibrational behavior of Co-MOF-74 upon gas adsorption. We show that the adsorption of H2 O leads to a characteristic shift of the peak maxima in the Raman spectra.

High-Flux Membranes Based on the Covalent Organic Framework COF-LZU1 for Selective Dye Separation by Nanofiltration.

Covalent organic frameworks (COFs) are attractive candidates for advanced water-treatment membranes owing to their high porosity and well-organized channel structures. Herein, the continuous two-dimensional imine-linked COF-LZU1 membrane with a thickness of only 400 nm was prepared on alumina tubes by in situ solvothermal synthesis. The membrane shows excellent water permeance (ca. 760 L m-2 h-1 MPa-1 ) and favorable rejection rates exceeding 90 % for water-soluble dyes larger than 1.2 nm. The water permeance through the COF-LZU1 membrane is much higher than that of most membranes with similar rejection rates. Long-time operation demonstrates the outstanding stability of the COF-LZU1 membrane. As the membrane has no selectivity for hydrated salt ions (selectivity <12 %), it is also suitable for the purification of dye products from saline solutions. The excellent performance and the outstanding water stability render the COF-LZU1 membrane an interesting system for water purification.

Hierarchical Nanostructures of Metal-Organic Frameworks Applied in Gas Separating ZIF-8-on-ZIF-67 Membranes.

Membranes from metal-organic frameworks (MOFs) are highly interesting for industrial gas separation applications. Strongly improved performances for carbon capture and H2 purification tasks in MOF membranes are obtained by using highly reproducable and very accuratly, hierarchically grown ZIF-8-on-ZIF-67 (ZIF-8@ZIF-67) nanostructures. To forgo hardly controllable solvothermal synthesis, particles and layers are prepared by self-assembling methods. It was possible for the first time to confirm ZIF-8-on-ZIF-67 membrane growth on rough and porous ceramic supports using the layer-by-layer deposition. Additionally, hierarchical particles are made in a fast RT synthesis with high monodispersity. Characterization of the hierarchical and epitaxial grown layers and particles is performed by SEM, TEM, EDXM and gas permeation. The system ZIF-8@ZIF-67 shows a nearly doubled H2 /CO2 separation factor, regardless of whether neat membrane or mixed-matrix-membrane in comparison to other MOF materials.

Switching Thin Films of Azobenzene-Containing Metal-Organic Frameworks with Visible Light.

Stimuli-responsive molecules change their properties when exposed to external signals, such as light, and enable the preparation of smart materials. UV light, which often destroys organic materials, is typically required for activating the desired response of photoswitchable compounds, significantly limiting the potential applications of light-operated smart materials. Herein, we present the first metal-organic framework (MOF), which enables reversible modulation of key properties upon irradiation with visible light only. The fluorinated azobenzene side groups in the MOF structure can be reversibly switched between the trans and cis state by green and violet light, avoiding UV light. It was demonstrated that the uptake of guest molecules by these MOF films can be switched in a fully remote-controlled way. The membrane separation of hydrogen/hydrocarbon mixtures was investigated. The light-induced changes of the MOF pore size result in the switching of the permeation and of the selection factor.

Tunable molecular separation by nanoporous membranes.

Metal-organic frameworks offer tremendous potential for efficient separation of molecular mixtures. Different pore sizes and suitable functionalizations of the framework allow for an adjustment of the static selectivity. Here we report membranes which offer dynamic control of the selectivity by remote signals, thus enabling a continuous adjustment of the permeate flux. This is realized by assembling linkers containing photoresponsive azobenzene-side-groups into monolithic, crystalline membranes of metal-organic frameworks. The azobenzene moieties can be switched from the trans to the cis configuration and vice versa by irradiation with ultraviolet or visible light, resulting in a substantial modification of the membrane permeability and separation factor. The precise control of the cis:trans azobenzene ratio, for example, by controlled irradiation times or by simultaneous irradiation with ultraviolet and visible light, enables the continuous tuning of the separation. For hydrogen:carbon-dioxide, the separation factor of this smart membrane can be steplessly adjusted between 3 and 8.

Comparative Study of MIL-96(Al) as Continuous Metal-Organic Frameworks Layer and Mixed-Matrix Membrane.

MIL-96(Al) layers were prepared as supported metal-organic frameworks membrane via reactive seeding using the α-alumina support as the Al source for the formation of the MIL-96(Al) seeds. Depending on the solvent mixture employed during seed formation, two different crystal morphologies, with different orientation of the transport-active channels, have been formed. This crystal orientation and habit is predefined by the seed crystals and is kept in the subsequent growth of the seeds to continuous layers. In the gas separation of an equimolar H2/CO2 mixture, the hydrogen permeability of the two supported MIL-96(Al) layers was found to be highly dependent on the crystal morphology and the accompanied channel orientation in the layer. In addition to the neat supported MIL-96(Al) membrane layers, mixed-matrix membranes (MMMs, 10 wt % filler loading) as a composite of MIL-96(Al) particles as filler in a continuous Matrimid polymer phase have been prepared. Five particle sizes of MIL-96(Al) between 3.2 µm and 55 nm were synthesized. In the preparation of the MIL-96(Al)/Matrimid MMM (10 wt % filler loading), the following preparation problems have been identified: The bigger micrometer-sized MIL-96(Al) crystals show a trend toward sedimentation during casting of the MMM, whereas for nanoparticles aggregation and recrystallization to micrometer-sized MIL-96(Al) crystals has been observed. Because of these preparation problems for MMM, the neat supported MIL-96(Al) layers show a relatively high H2/CO2 selectivity (≈9) and a hydrogen permeance approximately 2 magnitudes higher than that of the best MMM.