Ionic liquid facilitated melting of the metal-organic framework ZIF-8.

Hybrid glasses from melt-quenched metal-organic frameworks (MOFs) have been emerging as a new class of materials, which combine the functional properties of crystalline MOFs with the processability of glasses. However, only a handful of the crystalline MOFs are meltable. Porosity and metal-linker interaction strength have both been identified as crucial parameters in the trade-off between thermal decomposition of the organic linker and, more desirably, melting. For example, the inability of the prototypical zeolitic imidazolate framework (ZIF) ZIF-8 to melt, is ascribed to the instability of the organic linker upon dissociation from the metal center. Here, we demonstrate that the incorporation of an ionic liquid (IL) into the porous interior of ZIF-8 provides a means to reduce its melting temperature to below its thermal decomposition temperature. Our structural studies show that the prevention of decomposition, and successful melting, is due to the IL interactions stabilizing the rapidly dissociating ZIF-8 linkers upon heating. This understanding may act as a general guide for extending the range of meltable MOF materials and, hence, the chemical and structural variety of MOF-derived glasses.

Metal-organic framework and inorganic glass composites.

Metal-organic framework (MOF) glasses have become a subject of interest as a distinct category of melt quenched glass, and have potential applications in areas such as ion transport and sensing. In this paper we show how MOF glasses can be combined with inorganic glasses in order to fabricate a new family of materials composed of both MOF and inorganic glass domains. We use an array of experimental techniques to propose the bonding between inorganic and MOF domains, and show that the composites produced are more mechanically pliant than the inorganic glass itself.

Comparison of the ionic conductivity properties of microporous and mesoporous MOFs infiltrated with a Na-ion containing IL mixture.

IL@MOF (IL: ionic liquid; MOF: metal-organic framework) materials have been proposed as a candidate for solid-state electrolytes, combining the inherent non-flammability and high thermal and chemical stability of the ionic liquid with the host-guest interactions of the MOF. In this work, we compare the structure and ionic conductivity of a sodium ion containing IL@MOF composite formed from a microcrystalline powder of the zeolitic imidazolate framework (ZIF), ZIF-8 with a hierarchically porous sample of ZIF-8 containing both micro- and mesopores from a sol-gel synthesis. Although the crystallographic structures were shown to be the same by X-ray diffraction, significant differences in particle size, packing and morphology were identified by electron microscopy techniques which highlight the origins of the hierarchical porosity. After incorporation of Na0.1EMIM0.9TFSI (abbreviated to NaIL; EMIM = 1-ethyl-3-methylimidazolium; TFSI = bis(trifluoromethylsulfonyl)imide), the hierarchically porous composite exhibited a 40% greater filling capacity than the purely microporous sample which was confirmed by elemental analysis and digestive proton NMR. Finally, the ionic conductivity properties of the composite materials were probed by electrochemical impedance spectroscopy. The results showed that despite the 40% increased loading of NaIL in the NaIL@ZIF-8micro sample, the ionic conductivities at 25 °C were 8.4 × 10-6 and 1.6 × 10-5 S cm-1 for NaIL@ZIF-8meso and NaIL@ZIF-8micro respectively. These results exemplify the importance of the long range, continuous ion pathways contributed by the microcrystalline pores, as well as the limited contribution from the discontinuous mesopores to the overall ionic conductivity.

Sodium Ion Conductivity in Superionic IL-Impregnated Metal-Organic Frameworks: Enhancing Stability Through Structural Disorder.

Metal-organic frameworks (MOFs) are intriguing host materials in composite electrolytes due to their ability for tailoring host-guest interactions by chemical tuning of the MOF backbone. Here, we introduce particularly high sodium ion conductivity into the zeolitic imidazolate framework ZIF-8 by impregnation with the sodium-salt-containing ionic liquid (IL) (Na0.1EMIM0.9)TFSI. We demonstrate an ionic conductivity exceeding 2 × 10-4 S · cm-1 at room temperature, with an activation energy as low as 0.26 eV, i.e., the highest reported performance for room temperature Na+-related ion conduction in MOF-based composite electrolytes to date. Partial amorphization of the ZIF-backbone by ball-milling results in significant enhancement of the composite stability towards exposure to ambient conditions, up to 20 days. While the introduction of network disorder decelerates IL exudation and interactions with ambient contaminants, the ion conductivity is only marginally affected, decreasing with decreasing crystallinity but still maintaining superionic behavior. This highlights the general importance of 3D networks of interconnected pores for efficient ion conduction in MOF/IL blends, whereas pore symmetry is a less stringent condition.

Novel metal-organic framework materials: blends, liquids, glasses and crystal-glass composites.

Metal-organic frameworks (MOFs) are often, and incorrectly, believed to be purely crystalline solids. This Feature Article highlights a selection of highly disordered MOF-based materials. This disorder gives rise to numerous possibilities in the fabrication of new MOF materials, and presents an alternative method of novel materials discovery, outside of the synthesis of increasingly complex crystalline structures. The formation of liquid MOFs and resultant melt-quenched glasses is reviewed, along with several categories of novel MOF-based materials including blends, flux melted glasses and crystal-glass composites.

Membrane Scaffolds Enhance the Responsiveness and Stability of DNA-Based Sensing Circuits.

Target-induced DNA strand displacement is an excellent candidate for developing analyte-responsive DNA circuitry to be used in clinical diagnostics and synthetic biology. While most available technologies rely on DNA circuitry free to diffuse in bulk, here we explore the use of liposomes as scaffolds for DNA-based sensing nanodevices. Our proof-of-concept sensing circuit responds to the presence of a model target analyte by releasing a DNA strand, which in turn activates a fluorescent reporter. Through a combination of experiments and coarse-grained Monte Carlo simulations, we demonstrate that the presence of the membrane scaffold accelerates the process of oligonucleotide release and suppresses undesired leakage reactions, making the sensor both more responsive and robust.

Polymorphism in M(H2PO2)3 (M = V, Al, Ga) compounds with the perovskite-related ReO3 structure.

Trivalent metal hypophosphites with the general formula M(H2PO2)3 (M = V, Al, Ga) adopt the ReO3 structure, with each compound displaying two structural polymorphs. High-pressure synchrotron X-ray studies reveal a pressure-driven phase transition in Ga(H2PO2)3 that can be understood on the basis of ab initio thermodynamics.