A MOF Glass Membrane for Gas Separation

Metal–organic framework (MOF) glasses are promising candidates for membrane fabrication due to their significant porosity, the ease of processing, and most notably, the potential to eliminate the grain boundary that is unavoidable for polycrystalline MOF membranes. Herein, we developed a ZIF‐62 MOF glass membrane and exploited its intrinsic gas‐separation properties. The MOF glass membrane was fabricated by melt‐quenching treatment of an in situ solvothermally synthesized polycrystalline ZIF‐62 MOF membrane on a porous ceramic alumina support. The molten ZIF‐62 phase penetrated into the nanopores of the support and eliminated the formation of intercrystalline defects in the resultant glass membrane. The molecular sieving ability of the MOF membrane is remarkably enhanced via vitrification. The separation factors of the MOF glass membrane for H₂/CH₄, CO₂/N₂ and CO₂/CH₄ mixtures are 50.7, 34.5, and 36.6, respectively, far exceeding the Robeson upper bounds.     

Equibiaxial extension of a thermotropic liquid-crystalline polymer Flow induced orientation, relaxation of orientation, and strain recovery

The effects of equibiaxial extensional flow on the structural state of a thermotropic liquid crystal aromatic copolyester are studied through wide-angle X-ray scattering (WAXS), strain recovery above the melting point, and differential scanning calorimetry (D.S.C.). For that purpose, samples were melted, stretched and cooled to room temperature. WAXS patterns and strain recovery show that equibiaxial extension (achieved through the lubricated squeezing experiment) results in a planarly-oriented state, i.e. preferred molecular orientation perpendicular to the compression direction accompanied by random molecular orientation within the plane of extension. This flow-induced oriented state may relax partially if not prevented by stretching in the super-cooled liquid state (10-30 K below the melting point). Quenching immediately after deformation at a high temperature can also result in the retention of a high degree of orientation, but it lowers the degree of crystallinity. D.S.C. data show that low cooling rates and large extensions lead to the highest crystallinity. Strain recovery upon reheating is remarkably high for samples with high orientation. This large recovery is attributed to the elasticity of the macrostructure which is formed by the LCP molecules (structural elasticity) and not to the elasticity of the molecules.     

Coordination-Induced N−H Bond Splitting of Ammonia and Primary Amine of CuI−MOFs

We report a porous three-dimensional anionic tetrazolium based Cu^I−MOF 1 , which is capable of cleaving the N−H bond of ammonia and primary amine, as well as the O−H bond of H₂O along with spontaneous H₂ evolution. In the gas-solid phase reaction of 1 with ammonia and water vapor, Cu^I−MOF 1 was gradually oxidized to NH₂−Cu^II−MOF and OH−Cu^II−MOF, through single-crystal-to-single-crystal (SCSC) structural transformations, which was confirmed by XPS, PXRD and X-ray single-crystal diffraction. Density functional theory (DFT) demonstrated that Cu^I−MOF could lower N−H bond dissociation free energy of ammonia through coordination-induced bond weakening and promote H₂ evolution by the reduction potential of 1 . To our knowledge, this is the first example of MOFs that activate ammonia and amine in gas-solid manner.     

High-Temperature Quantum Tunneling and Hydrogen Bonding Rearrangements Characterize the Solid-Solid Phase Transitions in a Phosphonium-Based Protic Ionic Liquid

We report the complex phase behavior of the glass forming protic ionic liquid (PIL) d3-octylphosphonium bis(trifluoromethylsulfonyl)imide [C₈H₁₇PD₃][NTf₂] by means of solid-state NMR spectroscopy. Combined line shape and spin relaxation studies of the deuterons in the PD₃ group of the octylphosphonium cation allow to map and correlate the phase behavior for a broad temperature range from 71 K to 343 K. In the solid PIL at 71 K, we observed a static state, characterized by the first deuteron quadrupole coupling constant reported for PD₃ deuterons. A transition enthalpy of about 12 kJ mol⁻¹ from the static to the mobile state with increasing temperature suggests the breaking of a weak, charge-enhanced hydrogen bond between cation and anion. The highly mobile phase above 100 K exhibits an almost disappearing activation barrier, strongly indicating quantum tunneling. Thus, we provide first evidence of tunneling driven mobility of the hydrogen bonded P−D moieties in the glassy state of PILs, already at surprisingly high temperatures up to 200 K. Above 250 K, the mobile phase turns from anisotropic to isotropic motion, and indicates strong internal rotation of the PD₃ group. The analyzed line shapes and spin relaxation times allow us to link the structural and dynamical behavior at molecular level with the phase behavior beyond the DSC traces.     

Dielectric polarization of cross-linked poly(ethylene oxide)—phenomenology

Results of dielectric relaxation studies will be discussed. It turns out that competition of electric and structural relaxation coins permittivity and as a result conductivity mechanism at low temperature. It dominates long-ranging relaxation in the molten state. In the opposite limit of temperature, cross-linked poly(ethylene oxide) (PEO) with low mesh size can be transferred into super-cooled liquid state. Then, PEO behaves like a hydrogen-bonded liquid since crystallization is strongly suppressed. As a result, one observes slow Debye-like relaxation at low temperature. Beyond the low-frequency region, there appears an extended region between crossings of impedance components, where Z′ ≈ Z″ at acceptable approximation. It is coined by damped oscillation under action of the electric field. These effects lessen with increasing mesh size of the sample as clearly shown by M″(ω) spectra. The dipole moment of the PEO samples in molten state decreases only slightly with increasing mesh size.     

原子尺寸差异与非晶形成能力

采用分子动力学模拟技术，研究了纯Au及AuCu合金的熔化、非晶化和晶化过程.模拟结果表明,在冷却速率为5×1011 K•s－1至4×1012 K•s－1的范围内，液态Au总是形成晶体，且冷速越快，结晶温度越低；而AuCu合金则形成非晶，且冷速越快，非晶转变温度越高.验证了原子尺寸的不匹配有利于非晶形成这一规律.     

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

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.     

Thermal hysteresis in dithiadiazolyl and dithiazolyl radicals induced by supercooling of paramagnetic liquids close to room temperature: a study of F3CCNSSN and an interpretation of the behaviour of F3CCSNSCCF3

The trifluoromethyl-substituted dithiadiazolyl and dithiazolyl radicals, F3CCNSSN (1) and F3CCSNSCCF3 (2) associate through pi*-pi* covalent and electrostatic S delta+...N delta- interactions in the solid state, but melt with a dramatic volume increase to generate paramagnetic liquids; these radicals exhibit thermal hysteresis, which arises through a meta-stable super-cooled liquid state, close to room temperature.     

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

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.     

Introduction of an Ionic Liquid into the Micropores of a Metal–Organic Framework and Its Anomalous Phase Behavior

Controlling the dynamics of ionic liquids (ILs) is a significant issue for widespread use. Metal–organic frameworks (MOFs) are ideal host materials for ILs because of their small micropores and tunable host–guest interactions. Herein, we demonstrate the first example of an IL incorporated within the micropores of a MOF. The system studied consisted of EMI‐TFSA (1‐ethyl‐3‐methylimidazolium bis(trifluoromethylsulfonyl)amide) and ZIF‐8 (composed of Zn(MeIM)₂; H(MeIM)=2‐methylimidazole) as the IL and MOF, respectively. Construction of the EMI‐TFSA in ZIF‐8 was confirmed by X‐ray powder diffraction, nitrogen gas adsorption, and infrared absorption spectroscopy. Differential scanning calorimetry and solid‐state NMR measurements showed that the EMI‐TFSA inside the micropores demonstrated no freezing transition down to 123 K, whereas bulk EMI‐TFSA froze at 231 K. Such anomalous phase behavior originates from the nanosize effect of the MOF on the IL. This result provides a novel strategy for stabilizing the liquid phase of the ILs down to a lower temperature region.     

Ruthenium Complexation in an Aluminium Metal–Organic Framework and Its Application in Alcohol Oxidation Catalysis

A ruthenium trichloride complex has been loaded into an aluminium metal–organic framework (MOF), MOF‐253, by post‐synthetic modification to give MOF‐253‐Ru. MOF‐253 contains open bipyridine sites that are available to bind with the ruthenium complex. MOF‐253‐Ru was characterised by elemental analysis, N₂ sorption and X‐ray powder diffraction. This is the first time that a Ru complex has been coordinated to a MOF through post‐synthetic modification and used as a heterogeneous catalyst. MOF‐253‐Ru catalysed the oxidation of primary and secondary alcohols, including allylic alcohols, with PhI(OAc)₂ as the oxidant under very mild reaction conditions (ambient temperature to 40 °C). High conversions (up to >99 %) were achieved in short reaction times (1–3 h) by using low catalyst loadings (0.5 mol % Ru). In addition, high selectivities (>90 %) for aldehydes were obtained at room temperature. MOF‐253‐Ru can be recycled up to six times with only a moderate decrease in substrate conversion.     

Novel method to detect the volumetric glass --> liquid transition at high pressures: glycerol as a test case

We report a novel method of detecting the glass --> liquid transition at high pressures, which comprises measuring the relative volume change incurred upon heating glassy samples into the liquid state. We show data on glycerol in the pressure range 0.050-1.00 GPa to demonstrate the viability of the method. The reversible glass --> liquid transition is observed by means of a kink in the relative volume change on heating the sample isobarically, which is attributed to the glass --> liquid transition temperature Tg. This kink can only be observed in the second and subsequent heating cycles since it is superposed by a compaction in the first heating cycle. The isobaric thermal expansivity beta, which is closely related to the first derivative of this curve, shows the features expected for a glass --> liquid transition, including a sharp rise of beta(glass) in a narrow temperature interval to beta(viscous liquid) and an accompanying overshoot effect. Both Tg and the size of the overshoot effect vary in accordance with theory upon changing the ratio of cooling to heating rates. From the shape of this curve the onset, inflection, overshoot peak, and endpoint of the glass --> liquid transition can be extracted, which can be employed to calculate the reduced glass transition width as a measure for the fragility of the liquid. Comparison with literature data allows quantifying the accuracy of the liquid's thermal expansivity beta to be at least +/-10%, while the error in beta is significantly larger for the expansivity of the glassy state. The reproducibility of the glass --> liquid transition temperature Tg is better than +/-2 K. Our glycerol data confirms literature studies showing a nonlinear increase of Tg with increasing pressure (approximately 35 K/GPa on average), which is accompanied by an increase in fragility.     

Toward 3D printed hydrogen storage materials made with ABS‐MOF composites

The push to advance efficient, renewable, and clean energy sources has brought with it an effort to generate materials that are capable of storing hydrogen. Metal–organic framework materials (MOFs) have been the focus of many such studies as they are categorized for their large internal surface areas. We have addressed one of the major shortcomings of MOFs (their processibility) by creating and 3D printing a composite of acrylonitrile butadiene styrene (ABS) and MOF‐5, a prototypical MOF, which is often used to benchmark H₂ uptake capacity of other MOFs. The ABS‐MOF‐5 composites can be printed at MOF‐5 compositions of 10% and below. Other physical and mechanical properties of the polymer (glass transition temperature, stress and strain at the breaking point, and Young's modulus) either remain unchanged or show some degree of hardening due to the interaction between the polymer and the MOF. We do observe some MOF‐5 degradation through the blending process, likely due to the ambient humidity through the purification and solvent casting steps. Even with this degradation, the MOF still retains some of its ability to uptake H₂, seen in the ability of the composite to uptake more H₂ than the pure polymer. The experiments and results described here represent a significant first step toward 3D printing MOF‐5‐based materials for H₂ storage.     

Crystal Dynamics in Multi‐stimuli‐Responsive Entangled Metal–Organic Frameworks

An understanding of solid‐state crystal dynamics or flexibility in metal–organic frameworks (MOFs) showing multiple structural changes is highly demanding for the design of materials with potential applications in sensing and recognition. However, entangled MOFs showing such flexible behavior pose a great challenge in terms of extracting information on their dynamics because of their poor single‐crystallinity. In this article, detailed experimental studies on a twofold entangled MOF ( f‐MOF‐1) are reported, which unveil its structural response toward external stimuli such as temperature, pressure, and guest molecules. The crystallographic study shows multiple structural changes in f‐MOF‐1 , by which the 3 D net deforms and slides upon guest removal. Two distinct desolvated phases, that is, f‐MOF‐1 a and f‐MOF‐1 b , could be isolated; the former is a metastable one and transformable to the latter phase upon heating. The two phases show different gated CO₂ adsorption profiles. DFT‐based calculations provide an insight into the selective and gated adsorption behavior with CO₂ of f‐MOF‐1 b . The gate‐opening threshold pressure of CO₂ adsorption can be tuned strategically by changing the chemical functionality of the linker from ethanylene (?CH₂?CH₂?) in f‐MOF‐1 to an azo (?N=N?) functionality in an analogous MOF, f‐MOF‐2 . The modulation of functionality has an indirect influence on the gate‐opening pressure owing to the difference in inter‐net interaction. The framework of f‐MOF‐1 is highly responsive toward CO₂ gas molecules, and these results are supported by DFT calculations.     

A stable Co(II)-based metal-organic framework with dual-functional pyrazolate-carboxylate ligand: Construction and CO2 selective adsorption and fixation

By taking the functional advantages of both pyrazolate and carboxylate ligands, a unique dual-functional pyrazolate-carboxylate ligand acid, 4-(3,6-di(pyrazol-4-yl)-9-carbazol-9-yl)benzoic acid (H₃PCBA) was designed and synthesized. Using it, a new Co(II)-based metal-organic framework (MOF), Co₃(PCBA)₂(H₂O)₂ (BUT-75) has been constructed. It revealed a (3,6)-connected net based on the 6-connected linear trinuclear metal node, and showed good chemical stability in a wide pH range from 3 to 12 at room temperature, as well as in boiling water. Due to the presence of rich exposed Co(II) sites in pores, BUT-75 presented high selective CO₂ adsorption capacity over N₂ at 298 K. Simultaneously, it demonstrated fine catalytic performance for the cycloaddition of CO₂ with epoxides into cyclic carbonates under ambient conditions. This work has not only enriched the MOF community through integrating diverse functionalities into one ligand but also contributed a versatile platform for CO₂ fixation, thereby pushing MOF chemistry forward by stability enhancement and application expansion.     

High-Porosity Metal-Organic Framework Glasses

We report a synthetic strategy to link titanium-oxo (Ti-oxo) clusters into metal-organic framework (MOF) glasses with high porosity though the carboxylate linkage. A new series of MOF glasses was synthesized by evaporation of solution containing Ti-oxo clusters Ti₁₆O₁₆(OEt)₃₂, linkers, and m-cresol. The formation of carboxylate linkages between the Ti-oxo clusters and the carboxylate linkers was confirmed by Fourier-transform infrared (FT-IR) spectroscopy. The structural integrity of the Ti-oxo clusters within the glasses was evidenced by both X-ray absorption near edge structure (XANES) and ¹⁷O magic-angle spinning (MAS) NMR. After ligand exchange and activation, the fumarate-linked MOF glass, termed Ti-Fum, showed a N₂ Brunauer–Emmett–Teller (BET) surface areas of 923 m² g⁻¹, nearly three times as high as the phenolate-linked MOF glass with the highest BET surface area prior to this report.     

Thermodynamic Properties of a First-Generation Carbosilane Dendrimer with Terminal Phenylethyl Groups

The heat capacity of a first-generation carbosilane dendrimer with terminal phenylethyl groups as a function of temperature in the range from 6 to 520 K is studied for the first time via precision adiabatic vacuum calorimetry and differential scanning calorimetry. Physical transformations, such as low-temperature structural anomaly and glass transition are detected in the above-mentioned range of temperatures, and their standard thermodynamic characteristics are determined and analyzed. The standard thermodynamic functions of the studied dendrimer in the range of T → 0 to 520 K are calculated from the experimental data, as is the standard entropy in the devitrified state at T = 298.15 K. The standard thermodynamic characteristics of the carbosilane dendrimers studied in this work and earlier are compared.     

Metal-Organic Framework Glass Catalysts from Melting Glass-Forming Cobalt-Based Zeolitic Imidazolate Framework for Boosting Photoelectrochemical Water Oxidation

Sluggish oxygen evolution kinetics and serious charge recombination restrict the development of photoelectrochemical (PEC) water splitting. The advancement of novel metal–organic frameworks (MOFs) catalysts bears practical significance for improving PEC water splitting performance. Herein, a MOF glass catalyst through melting glass-forming cobalt-based zeolitic imidazolate framework (Co-a_gZIF-62) was introduced on various metal oxide (MO: Fe₂O₃, WO₃ and BiVO₄) semiconductor substrates coupled with NiO hole transport layer, constructing the integrated Co-a_gZIF-62/NiO/MO photoanodes. Owing to the excellent conductivity, stability and open active sites of MOF glass, Co-a_gZIF-62/NiO/MO photoanodes exhibit a significantly enhanced photoelectrochemical water oxidation activity and stability in comparison to pristine MO photoanodes. From experimental analyses and density functional theory calculations, Co-a_gZIF-62 can effectively promote charge transfer and separation, improve carrier mobility, accelerate the kinetics of oxygen evolution reaction (OER), and thus improve PEC performance. This MOF glass not only serves as an excellent OER cocatalyst on tunable photoelectrodes, but also enables promising opportunities for PEC devices for solar energy conversion.     

Boosting the Catalytic Performance of Metal–Organic Frameworks for Steroid Transformations by Confinement within a Mesoporous Scaffold

Solid‐state crystallization achieves selective confinement of metal–organic framework (MOF) nanocrystals within mesoporous materials, thereby rendering active sites more accessible compared to the bulk‐MOF and enhancing the chemical and mechanical stability of MOF nanocrystals. (Zr)UiO‐66(NH₂)/SiO₂ hybrid materials were tested as efficient and reusable heterogeneous catalysts for the synthesis of steroid derivatives, outperforming the bulk (Zr)UiO‐66(NH₂) MOF. A clear correlation between the catalytic activity of the dispersed Zr sites present in the confined MOF, and the loading of the mesoporous SiO₂, is demonstrated for steroid transformations.     

Preserving Macroporosity in Type III Porous Liquids

Preserving large permanent pore structures in a fluid may endow conventional liquids with emergent physical properties. However, such materials are challenging to make because of the tendency of the pores to be filled and occupied by the solvent molecules. Here, we report the design and synthesis of the first Type III porous liquid (PL) containing uniform yet stable 480 nm cavities. This was achieved by first constructing a single crystalline hollow metal–organic framework (MOF), UiO-66-NH₂, through chemical etching. The thin yet defect-free MOF shell effectively excludes the bulky poly(dimethylsiloxane) solvent molecules from entering the cavity through its 4 Å aperture, resulting in the preservation of both micro- and macroporosity in the PL. These enormous void spaces allow the PL to reversibly host and release up to 27 wt % water for up to 10 cycles. The switching between the “dry” state and the “wet” state led to a large changes of the thermal conductivity of the PL from 0.140 to 0.256 W m⁻¹ K⁻¹, affording a guest-responsive liquid thermal switch with a switching ratio of 1.8.