Quantification of gas-accessible microporosity in metal-organic framework glasses

Metal-organic framework (MOF) glasses are a new class of microporous glass materials with immense potential for applications ranging from gas separation to optics and solid electrolytes. Due to the inherent difficulty to determine the atomistic structure of amorphous glasses, the intrinsic structural porosity of MOF glasses is only poorly understood. In this work, the porosity features of a series of prototypical MOF glass formers from the family of zeolitic imidazolate frameworks (ZIFs) and their corresponding glasses is investigated comprehensively. CO2 gas sorption at 195 K allows to follow the evolution of microporosity when transforming from the crystalline to the glassy state of these materials. Based on these data, the pore volume and the real density of the ZIF glasses is quantified for the first time. Additional hydrocarbon sorption data (n-butane, propane and propylene) together with X-ray total scattering experiments prove that the porosity features (in particular the pore size and the pore limiting diameter) of the ZIF glasses depend on the types of organic linkers present in the glass network. This allows formulating first design principles for a targeted tuning of the intrinsic microporosity of MOF glasses. Importantly, these principles are counterintuitive and contrary to established porosity design concepts for crystalline MOFs but show similarities to strategies previously developed for porous polymers.

Exploration of glassy state in Prussian blue analogues

Prussian blue analogues (PBAs), a class of microporous crystalline coordination frameworks, are long known for their diverse properties in porosity, magnetic, charge transport, catalysis, optics, and more. Versatile structural composition and the ability to control defect ordering through synthetic conditions offer opportunities to manipulate the functionality in the crystalline state. However, developments in Prussian blue analogues (PBAs) have primarily revolved around the ordered crystalline state, and the glassy state of PBAs has not yet been explored. Here we report the discovery of a disordered glassy state of the PBA via mechanically induced crystal–glass transformation. We found the preservation of metal–ligand–metal connectivity, confirming the short-range order and semiconductor behaviour, exhibiting an electronic conductivity value of 0.31 mS cm−1 at 50 ˚C. Mechanical-induced glass transformation also triggers changes in electronic states, where electroneutrality is compensated by introducing unconventional CN− vacancies. Partial disorders and ligand vacancies in recrystallized PBA give rise to an enhanced porosity, inaccessible in the crystalline parent. The present work also established a correlation between the mechanical stress required to initiate crystal–glass transformation and intrinsic mechanical properties, which are controlled by the vacancy/defect content, the presence of interstitial water, and the overall composition of PBAs.

Vitrification Solutions for Plant Cryopreservation: Modification and Properties

Many plants cannot vitrify themselves because they lack glassy state-inducing substances and/or have high water content. Therefore, cryoprotectants are used to induce vitrification. A cryoprotectant must have at least the following primary abilities: high glass-forming property, dehydration strength on a colligative basis to dehydrate plant cells to induce the vitrification state, and must not be toxic for plants. This review introduces the compounds used for vitrification solutions (VSs), their properties indicating a modification of different plant vitrification solutions, their modifications in the compounds, and/or their concentration. An experimental comparison is listed based on the survival or regeneration rate of one particular species after using more than three different VSs or their modifications. A brief overview of various cryopreservation methods using the Plant Vitrification Solution (PVS) is also included. This review can help in alert researchers to newly introduced PVSs for plant vitrification cryoprotocols, their properties, and the choice of their modifications in the compounds and/or their concentration.

Vitrification Ability of Combined and Single Cryoprotective Agents

Cryoprotective agents (CPA) are an important part of many current vitrification methods. The vitrification ability of CPAs influences the probability of the glass transition and water crystallization occurrence. Thermal characteristics and the vitrification ability of two combined CPAs (PVS2 and PVS3), common plant vitrification solutions, and four single CPAs (ethylene glycol, DMSO, glycerol, and sucrose), the components of the mentioned PVSs, were evaluated utilizing a differential scanning calorimetry (DSC) during standard cooling/warming rates of 10 °C min−1. The effect of solute concentration on their vitrification ability was shown in the CPAs tested. Four typical concentration regions at which the glassy state and/or crystallization occurred were defined. We suggest the solute concentration of 0.7 g g−1 as the universal vitrification concentration, characterized by an actual Tg of CPA solution and limited water crystallization. Knowledge of the thermal properties of CPAs allows the design of new combined CPAs with the required vitrification ability respecting the cryopreservation method used and the characteristics of the cryopreserved sample.

Peek Inside the Water Mixtures of Ionic Liquids at Molecular Level: Microscopic Properties Probed by EPR Spectroscopy

Many ionic liquids (ILs) can be mixed with water, forming either true solutions or emulsions. This favors their applications in many respects, but at the same time might strongly alter their physicochemical properties. A number of methods exist for studying the macroscopic properties of such mixtures, whereas understanding their characteristics at micro/nanoscale is rather challenging. In this work we investigate microscopic properties, such as viscosity and local structuring, in binary water mixtures of IL [Bmim]BF4 in liquid and glassy states. For this sake, we use continuous wave and pulse electron paramagnetic resonance (EPR) spectroscopy with dedicated spin probes, located preferably in IL-rich domains or distributed in IL- and water-rich domains. We demonstrate that the glassy-state nanostructuring of IL-rich domains is very similar to that in neat ILs. At the same time, in liquid state the residual water makes local viscosity in IL-rich domains noticeably different compared to neat ILs, even though the overwhelming amount of water is contained in water-rich domains. These results have to be taken into account in various applications of IL-water mixtures, especially in those cases demanding the combinations of optimum micro- and macroscopic characteristics.

Prediction of Second Melting Temperatures Already Observed in Pure Elements by Molecular Dynamics Simulations

A second melting temperature occurs at a temperature Tn+ higher than Tm in glass-forming melts after heating them from their glassy state. The melting entropy is reduced or increased depending on the thermal history and on the presence of antibonds or bonds up to Tn+. Recent MD simulations show full melting at Tn+ = 1.119Tm for Zr, 1.126Tm for Ag, 1.219Tm for Fe and 1.354Tm for Cu. The non-classical homogeneous nucleation model applied to liquid elements is based on the increase of the Lindemann coefficient with the heating rate. The glass transition at Tg and the nucleation temperatures TnG of glacial phases are successfully predicted below and above Tm. The glass transition temperature Tg increases with the heating rate up to Tn+. Melting and crystallization of glacial phases occur with entropy and enthalpy reductions. A universal law relating Tn+ and TnG around Tm shows that TnG cannot be higher than 1.293Tm for Tn+= 1.47Tm. The enthalpies and entropies of glacial phases have singular values, corresponding to the increase of percolation thresholds with Tg and TnG above the Scher and Zallen invariant at various heating and cooling rates. The G-phases are metastable up to Tn+ because the antibonds are broken by homogeneous nucleation of bonds.

Formability and Magnetic Properties of the Binary Nd-Co Amorphous Alloys

In this paper, binary Nd-Co alloys with compositional range from Nd72.5Co27.5 to Nd50Co50 were successfully vitrified into glassy state by a melt-spinning method. The glass formability of the metallic glasses (MGs) was studied and the best glass former in the binary Nd-Co alloys was obtained. Magnetic properties of the MGs were measured. The compositional dependence of Curie temperature of the MGs was observed. The mechanism for the spin-glass-like behaviors and high coercivity at low temperature, and their influence on the magnetic entropy change of the MGs, were investigated.

Highly Conducting Li(Fe1−xMnx)0.88V0.08PO4 Cathode Materials Nanocrystallized from the Glassy State (x = 0.25, 0.5, 0.75)

This study showed that thermal nanocrystallization of glassy analogs of LiFe1−xMnxPO4 (with the addition of vanadium for improvement of glass forming properties) resulted in highly conducting materials that may be used as cathodes for Li-ion batteries. The glasses and nanomaterials were studied with differential thermal analysis, X-ray diffractometry, and impedance spectroscopy. The electrical conductivity of the nanocrystalline samples varied, depending on the composition. For x=0.5, it exceeded 10−3 S/cm at room temperature with an activation energy as low as 0.15 eV. The giant and irreversible increase in the conductivity was explained on the basis of Mott’s theory of electron hopping and a core-shell concept. Electrochemical performance of the active material with x=0.5 was also reported.