Hydrogen-Bonding Interactions in Hybrid Aqueous/Nonaqueous Electrolytes Enable Low-Cost and Long-Lifespan Sodium-Ion Storage.

Although "water-in-salt" electrolytes have opened a new pathway to expand the electrochemical stability window of aqueous electrolytes, the electrode instability and irreversible proton co-insertion caused by aqueous media still hinder the practical application, even when using exotic fluorinated salts. In this study, an accessible hybrid electrolyte class based on common sodium salts is proposed, and crucially an ethanol-rich media is introduced to achieve highly stable Na-ion electrochemistry. Here, ethanol exerts a strong hydrogen-bonding effect on water, simultaneously expanding the electrochemical stability window of the hybridized electrolyte to 2.5 V, restricting degradation activities, reducing transition metal dissolution from the cathode material, and improving electrolyte-electrode wettability. The binary ethanol-water solvent enables the impressive cycling of sodium-ion batteries based on perchlorate, chloride, and acetate electrolyte salts. Notably, a Na0.44MnO2 electrode exhibits both high capacity (81 mAh g-1) and a remarkably long cycle life >1000 cycles at 100 mA g-1 (a capacity decay rate per cycle of 0.024%) in a 1 M sodium acetate system. The Na0.44MnO2/Zn full cells also show excellent cycling stability and rate capability in a wide temperature range. The gained understanding of the hydrogen-bonding interactions in the hybridized electrolyte can provide new battery chemistry guidelines in designing promising candidates for developing low-cost and long-lifespan batteries based on other (Li+, K+, Zn2+, Mg2+, and Al3+) systems.

Origin of giant negative piezoelectricity in a layered van der Waals ferroelectric.

Recent research on piezoelectric materials is predominantly devoted to enhancing the piezoelectric coefficient, but overlooks its sign, largely because almost all of them exhibit positive longitudinal piezoelectricity. The only experimentally known exception is ferroelectric polymer poly(vinylidene fluoride) and its copolymers, which condense via weak van der Waals (vdW) interaction and show negative piezoelectricity. Here we report quantitative determination of giant intrinsic negative longitudinal piezoelectricity and electrostriction in another class of vdW solids-two-dimensional (2D) layered ferroelectric CuInP2S6. With the help of single crystal x-ray crystallography and density-functional theory calculations, we unravel the atomistic origin of negative piezoelectricity in this system, which arises from the large displacive instability of Cu ions coupled with its reduced lattice dimensionality. Furthermore, the sizable piezoelectric response and negligible substrate clamping effect of the 2D vdW piezoelectric materials warrant their great potential in nanoscale, flexible electromechanical devices.

Synthesis and Electronic Properties of Novel 5,7-Diazapentacene Derivatives.

A route to the synthesis of novel 5,7-diazapentacenes and some preliminary studies on their properties is reported. A single crystal X-ray diffraction study of the dihexyl derivative showed it had formed a dimer during the analysis. The materials possess lower lying frontier orbitals than pentacene and may have potential applications in organic electronic devices. This synthetic method may be applicable to the synthesis of other azaacenes.

Hydrolytic stability in hemilabile metal-organic frameworks.

Highly porous metal-organic frameworks (MOFs), which have undergone exciting developments over the past few decades, show promise for a wide range of applications. However, many studies indicate that they suffer from significant stability issues, especially with respect to their interactions with water, which severely limits their practical potential. Here we demonstrate how the presence of 'sacrificial' bonds in the coordination environment of its metal centres (referred to as hemilability) endows a dehydrated copper-based MOF with good hydrolytic stability. On exposure to water, in contrast to the indiscriminate breaking of coordination bonds that typically results in structure degradation, it is non-structural weak interactions between the MOF's copper paddlewheel clusters that are broken and the framework recovers its as-synthesized, hydrated structure. This MOF retained its structural integrity even after contact with water for one year, whereas HKUST-1, a compositionally similar material that lacks these sacrificial bonds, loses its crystallinity in less than a day under the same conditions.

Cost-effective 17O enrichment and NMR spectroscopy of mixed-metal terephthalate metal-organic frameworks.

17O solid-state NMR spectroscopy is employed to investigate the cation disorder in metal-organic frameworks containing two different types of metal cations. Although NMR offers exquisite sensitivity to the local, atomic-scale structure, making it an ideal tool for the characterisation of disordered materials, the low natural abundance of 17O (0.037%) necessitates expensive isotopic enrichment to acquire spectra on a reasonable timescale. Using dry gel conversion and a novel steaming method we show that cost-effective and atom-efficient enrichment of MOFs is possible, and that high-resolution 17O NMR spectra are sensitive both to the structural forms of the MOF and the presence of guest molecules. For mixed-metal forms of MIL-53, NMR can also provide information on the final composition of the materials (notably different to that of the initial starting material) and the preference for cation clustering/ordering within the MOFs. For Al, Ga MIL-53, the distribution of cations results in a mixed-pore form upon exposure to water, unlike the different structures seen for the corresponding end members. This work shows that as good levels of enrichment can be achieved at reasonable cost, 17O NMR spectroscopy should be an invaluable tool for the study of these important functional materials.

In situ solid-state NMR and XRD studies of the ADOR process and the unusual structure of zeolite IPC-6.

The assembly-disassembly-organization-reassembly (ADOR) mechanism is a recent method for preparing inorganic framework materials and, in particular, zeolites. This flexible approach has enabled the synthesis of isoreticular families of zeolites with unprecedented continuous control over porosity, and the design and preparation of materials that would have been difficult-or even impossible-to obtain using traditional hydrothermal techniques. Applying the ADOR process to a parent zeolite with the UTL framework topology, for example, has led to six previously unknown zeolites (named IPC-n, where n = 2, 4, 6, 7, 9 and 10). To realize the full potential of the ADOR method, however, a further understanding of the complex mechanism at play is needed. Here, we probe the disassembly, organization and reassembly steps of the ADOR process through a combination of in situ solid-state NMR spectroscopy and powder X-ray diffraction experiments. We further use the insight gained to explain the formation of the unusual structure of zeolite IPC-6.

Expansion of the ADOR Strategy for the Synthesis of Zeolites: The Synthesis of IPC-12 from Zeolite UOV.

The assembly-disassembly-organization-reassembly (ADOR) process has been used to disassemble a parent zeolite with the UOV structure type and then reassemble the resulting layers into a novel structure, IPC-12. The structure of the material has previously been predicted computationally and confirmed in our experiments using X-ray diffraction and atomic resolution STEM-HAADF electron microscopy. This is the first successful application of the ADOR process to a material with porous layers.

A space-time skew-t model for threshold exceedances.

To assess the compliance of air quality regulations, the Environmental Protection Agency (EPA) must know if a site exceeds a pre-specified level. In the case of ozone, the level for compliance is fixed at 75 parts per billion, which is high, but not extreme at all locations. We present a new space-time model for threshold exceedances based on the skew-t process. Our method incorporates a random partition to permit long-distance asymptotic independence while allowing for sites that are near one another to be asymptotically dependent, and we incorporate thresholding to allow the tails of the data to speak for themselves. We also introduce a transformed AR(1) time-series to allow for temporal dependence. Finally, our model allows for high-dimensional Bayesian inference that is comparable in computation time to traditional geostatistical methods for large data sets. We apply our method to an ozone analysis for July 2005, and find that our model improves over both Gaussian and max-stable methods in terms of predicting exceedances of a high level.

Combined PDF and Rietveld studies of ADORable zeolites and the disordered intermediate IPC-1P.

The disordered intermediate of the ADORable zeolite UTL has been structurally confirmed using the pair distribution function (PDF) technique. The intermediate, IPC-1P, is a disordered layered compound formed by the hydrolysis of UTL in 0.1 M hydrochloric acid solution. Its structure is unsolvable by traditional X-ray diffraction techniques. The PDF technique was first benchmarked against high-quality synchrotron Rietveld refinements of IPC-2 (OKO) and IPC-4 (PCR) - two end products of IPC-1P condensation that share very similar structural features. An IPC-1P starting model derived from density functional theory was used for the PDF refinement, which yielded a final fit of Rw = 18% and a geometrically reasonable structure. This confirms the layers do stay intact throughout the ADOR process and shows PDF is a viable technique for layered zeolite structure determination.

Coordination polymers of 5-substituted isophthalic acid.

The synthesis and characterisation of five coordination polymers - Ni2(mip)2(H2O)8·2H2O (1), Zn6(mip)5(OH)2(H2O)4·7.4H2O (2), Zn6(mip)5(OH)2(H2O)2·4H2O (3), Mn(HMeOip)2 (4), and Mn3(tbip)2(Htbip)2(EtOH)2 (5) - are reported. Preliminary nitric oxide release data on compounds 2 and 3 are also given.

Coordination polymers of Zn(II) and 5-methoxy isophthalate.

Solvothermal reaction of Zn(OAc)2 and 5-methoxy isophthalic acid (H2MeOip) in aqueous alcohols ROH (R = H, Me, Et, or (i)Pr) affords four different novel coordination polymers. Zn2(HMeOip)(MeOip)(OAc) (1) forms as a 1D 'ribbon of rings' polymer. Zn6(MeOip)4.5(HMeOip)(OH)2(H2O)2·5.5H2O (2) crystallises as a complex 3D framework. Zn(MeOip)(H2O)2 H2O (3) is a 1D coordination polymer that contains almost planar strips of Zn(MeOip). compound 4, Zn5(MeOip)4(OH)2(H2O)4·H2O, obtained from aqueous (i)PrOH, crystallises as a 2D polymer containing two crystallographically distinct Zn5(OH)2 clusters. Preliminary nitric oxide release experiments have been conducted.

Copper(II) fluorophosphates.

Eleven new copper fluorophosphate frameworks have been synthesised hydrothermally in a fluoride-rich medium, through the use of CuF(2) HPF(6) and monovalent metal fluorides as reactants. Products have been structurally characterised using single crystal X-ray diffraction. Reaction in fluoride-rich conditions produces chain, layer and three dimensional framework structures containing new and unusual structural features based on the linking of PO(3)F, PO(2)(OH,F)(2) and Cu(O,F)(n) polyhedra (n = 4-6). Analysis of these structures, in terms of the copper coordination environments and their linkage dimensionalities, shows that these features are dependent on fluoride-content of the reaction medium and, therefore, the level of fluoride ion incorporation into the product materials. Structures exhibiting inter-layer spaces and channels frequently have these lined by terminal fluoride anions of the PO(3)F, PO(2)(OH,F)(2) and Cu(O,F)(n) polyhedra.