To date, only several microporous, and even fewer nanoporous, glasses have been produced, always via post synthesis acid treatment of phase separated dense materials, e.g. Vycor glass. In comparison, high internal surface areas are readily achieved in crystalline materials, such as metal-organic frameworks (MOFs). It has recently been discovered that a new family of melt quenched glasses can be produced from MOFs, though they have thus far have lacked the accessible and intrinsic porosity of their crystalline precursors. Here, we report the first glasses that are permanently, and reversibly porous toward incoming gases, without post synthetic treatment. We characterized the structure of these glasses using a range of experimental techniques, and demonstrate pores in the 4-8 angstrom range. The discovery of MOF-glasses with permanent accessible porosity reveals a new category of porous glass materials, that are potentially elevated beyond conventional inorganic and organic porous glasses, by their diversity and tunability.

To date, only several microporous, and even fewer nanoporous, glasses have been produced, always via post synthesis acid treatment of phase separated dense materials, e.g. Vycor glass. In contrast, high internal surface areas are readily achieved in crystalline materials, such as metal-organic frameworks (MOFs). It has recently been discovered that a new family of melt quenched glasses can be produced from MOFs, though they have thus far lacked the accessible and intrinsic porosity of their crystalline precursors. Here, we report the first glasses that are permanently and reversibly porous toward incoming gases, without post-synthetic treatment. We characterize the structure of these glasses using a range of experimental techniques, and demonstrate pores in the range of 4 – 8 Å. The discovery of MOF glasses with permanent accessible porosity reveals a new category of porous glass materials that are elevated beyond conventional inorganic and organic porous glasses by their diversity and tunability.

The liquid and glass states of metal–organic frameworks (MOFs) have recently become of interest due to the potential for liquid-phase separations and ion transport, alongside the fundamental nature of the latter as a new, fourth category of melt-quenched glass. Here we show that the MOF liquid state can be blended with another MOF component, resulting in a domain structured MOF glass with a single, tailorable glass transition. Intra-domain connectivity and short range order is confirmed by nuclear magnetic resonance spectroscopy and pair distribution function measurements. The interfacial binding between MOF domains in the glass state is evidenced by electron tomography, and the relationship between domain size and Tg investigated. Nanoindentation experiments are also performed to place this new class of MOF materials into context with organic blends and inorganic alloys.

We show flux melting by using a liquid MOF as a solvent for a secondary, non-melting MOF component.

A high performance vanadium-doped LiFePO4 (LFP) electrode is synthesized using a continuous hydrothermal method at a rate of 6 kg per day. The supercritical water solvent rapidly generates core/shell nanoparticles with a thin, continuous carbon coating on the surface of LFP, which aids electron transport dynamics across the particle surface. Vanadium dopant concentration has a profound effect on the performance of LFP, where the composition LiFe0.95V0.05PO4 achieves a specific discharge capacity which is among the highest in the literature (119 mA h g-1 at a discharge rate of 1500 mA g-1). Additionally, a combination of Xray absorption spectroscopy analysis and hybrid-exchange density functional theory suggest that vanadium ions replace both phosphorous and iron in the structure, thereby facilitating Li + diffusion due to Li + vacancy generation and changes in the crystal structure.

<div>Recent demonstrations of melting in the metal-organic framework (MOF) family have created</div><div>interest in the interfacial domain between inorganic glasses and amorphous organic polymers. The</div><div>chemical and physical behaviour of porous hybrid liquids and glasses is of particular interest,</div><div>though opportunities are limited by the inaccessible melting temperatures of many MOFs. Here,</div><div>we show that the synthetic processing technique of flux melting, ‘borrowed’ from the inorganic</div><div>domain, may be applied to MOFs in order to melt materials which do not possess an accessible</div><div>liquid state in their pure form. We employ the high-temperature liquid state of one MOF as a solvent</div><div>for a secondary, non-melting MOF component. Differential scanning calorimetry, small- and wideangle</div><div>X-ray scattering, electron microscopy and X-ray total scattering techniques are used to show</div><div>the flux melting of the crystalline component within the liquid. Gas adsorption and positron</div><div>annihilation lifetime spectroscopy measurements show that this results in enhanced, accessible</div><div>porosity to a range of guest molecules, in the resultant flux melted MOF glass.</div>

Assembly of permanently porous metal-organic polyhedra/cages (MOPs) with bifunctional linkers leads to soft supramolecular networks featuring both porosity and processability. However, the amorphous nature of such soft materials complicates their...

The phase behavior and molecular ordering of hexakishexyloxy triphenylene (HAT6) DLCs under cylindrical nanoconfinement, for nanopore diameters ranging from 161 nm down to 12 nm, are studied utilizing differential scanning calorimetry (DSC) and dielectric spectroscopy (DS).