Interzeolite Transformation from FAU-to-EDI Type of Zeolite.

This study reports for the first time the transformation of the pre-made FAU type of zeolite to the EDI type of zeolite. The concentration of the KOH solution controls this interzeolite transformation, which unusually occurs at both room temperature and under hydrothermal conditions. The transformation involves the amorphization and partial dissolution of the parent FAU phase, followed by the crystallization of EDI zeolite. At room temperature, the transformation (11-35 days) provides access to well-shaped nano-sized crystals and hollow hierarchical particles while the hydrothermal synthesis results in faster crystallization (6-27 h). These findings reveal an example of an interzeolite transformation to a potassium zeolite that lacks common composite building units with the parent zeolite phase. Finally, this work also demonstrates the first room-temperature synthesis of EDI zeolite from a gel precursor.

High Performance Ternary Solid Polymer Electrolytes Based on High Dielectric Poly(vinylidene fluoride) Copolymers for Solid State Lithium-Ion Batteries.

Renewable energy sources require efficient energy storage systems. Lithium-ion batteries stand out among those systems, but safety and cycling stability problems still need to be improved. This can be achieved by the implementation of solid polymer electrolytes (SPE) instead of the typically used separator/electrolyte system. Thus, ternary SPEs have been developed based on poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) and poly(vinylidene fluoride-trifluoroethylene-chlorofluoroethylene), P(VDF-TrFE-CFE) as host polymers, clinoptilolite (CPT) zeolite added to stabilize the battery cycling performance, and ionic liquids (ILs) (1-butyl-3-methylimidazolium thiocyanate ([BMIM][SCN])), 1-methyl-1-propylpyrrolidinium bis(trifluoromethylsulfonyl)imide ([PMPyr][TFSI]) or lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), incorporated to increase the ionic conductivity. The samples were processed by doctor blade with solvent evaporation at 160 °C. The nature of the polymer matrix and fillers affect the morphology and mechanical properties of the samples and play an important role in electrochemical parameters such as ionic conductivity value, electrochemical window stability, and lithium-transference number. The best ionic conductivity (4.2 × 10-5 S cm-1) and lithium transference number (0.59) were obtained for the PVDF-HFP-CPT-[PMPyr][TFSI] sample. Charge-discharge battery tests at C/10 showed excellent battery performance with values of 150 mAh g-1 after 50 cycles, regardless of the polymer matrix and IL used. In the rate performance tests, the best SPE was the one based on the P(VDF-TrFE-CFE) host polymer, with a discharge value at C-rate of 98.7 mAh g-1, as it promoted ionic dissociation. This study proves for the first time the suitability of P(VDF-TrFE-CFE) as SPE in lithium-ion batteries, showing the relevance of the proper selection of the polymer matrix, IL type, and lithium salt in the formulation of the ternary SPE, in order to optimize solid-state battery performance. In particular, the enhancement of the ionic conductivity provided by the IL and the effect of the high dielectric constant polymer P(VDF-TrFE-CFE) in improving battery cyclability in a wide range of discharge rates must be highlighted.

Influence of Solvent Evaporation Temperature on the Performance of Ternary Solid Polymer Electrolytes Based on Poly(vinylidene fluoride-co-hexafluoropropylene) Combining an Ionic Liquid and a Zeolite.

Solid polymer electrolytes (SPEs) will allow improving safety and durability in next-generation solid-state lithium-ion batteries (LIBs). Within the SPE class, ternary composites are a suitable approach as they provide high room-temperature ionic conductivity and excellent cycling and electrochemical stability. In this work, ternary SPEs based on poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) as a polymer host, clinoptilolite (CPT) zeolite, and 1-butyl-3-methylimidazolium thiocyanate ([Bmim][SCN])) ionic liquid (IL) as fillers were produced by solvent evaporation at different temperatures (room temperature, 80, 120, and 160 °C). Solvent evaporation temperature affects the morphology, degree of crystallinity, and mechanical properties of the samples as well as the ionic conductivity and lithium transference number. The highest ionic conductivity (1.2 × 10-4 S·cm-1) and lithium transference number (0.66) have been obtained for the SPE prepared at room temperature and 160 °C, respectively. Charge-discharge battery tests show the highest value of discharge capacity of 149 and 136 mAh·g-1 at C/10 and C/2 rates, respectively, for the SPE prepared at 160 °C. We conclude that the fine control of the solvent evaporation temperature during the preparation of the SPE allows us to optimize solid-state battery performance.

Indium silicate with an imandrite-type structure.

This work reports the synthesis and characterization of novel zeolite-like indium silicate MS-2 (Minho-Sofia, solid number 2). The structure of this material is analogous to that of the mineral imandrite (Na6Ca1.5FeSi6O18), with In instead of Fe in the octahedral position. MS-2 is the first structurally confirmed indium silicate prepared under mild hydrothermal conditions and the only synthetic indium silicate related to the lovozerite mineral group. MS-2 (Na6.23Ca1.62In0.68Si6O18) exhibits significant indium deficiency in the octahedral position thus having the highest Si/In (8.8) ratio among the known indium silicates. The framework consists of occupationally disordered InO6 octahedra interconnected by 6-membered rings of [Si6O18] tetrahedra. The three-dimensional (3D) tunnel system is occupied by Na+ and Ca2+ charge-balancing ions. The low framework density (16.2 FC/1000 Å3) and high thermal stability (up to 900 °C) are comparable to other molecular sieves.

High-Performance Room Temperature Lithium-Ion Battery Solid Polymer Electrolytes Based on Poly(vinylidene fluoride-co-hexafluoropropylene) Combining Ionic Liquid and Zeolite.

The demand for more efficient energy storage devices has led to the exponential growth of lithium-ion batteries. To overcome the limitations of these systems in terms of safety and to reduce environmental impact, solid-state technology emerges as a suitable approach. This work reports on a three-component solid polymer electrolyte system based on poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), the ionic liquid 1-butyl-3-methylimidazolium thiocyanate ([BMIM][SCN]), and clinoptilolite zeolite (CPT). The influences of the preparation method and of the dopants on the electrolyte stability, ionic conductivity, and battery performance were studied. The developed electrolytes show an improved room temperature ionic conductivity (1.9 × 10-4 S cm-1), thermal stability (up to 300 °C), and mechanical stability. The corresponding batteries exhibit an outstanding room temperature performance of 160.3 mAh g-1 at a C/15-rate, with a capacity retention of 76% after 50 cycles. These results represent a step forward in a promising technology aiming the widespread implementation of solid-state batteries.

Three-Dimensional (3D) Microporous Iron Silicate with an Imandrite Type of Structure.

Small-pore iron silicate MS-1 (Minho-Sofia, solid number 1) with a 3D porous system, an analogue of the rare mineral imandrite, has been synthesized and characterized. This material is the lowest framework density iron silicate, one of the most siliceous (Si/Fe = 6) iron silicates, the first iron cyclosilicate achieved at hydrothermal conditions, and the only synthetic iron-based member of the lovozerite mineral group.

Room temperature synthesis of Bi25FeO39 and hydrothermal kinetic relations between sillenite- and distorted perovskite-type bismuth ferrites.

The time-dependent study at mild hydrothermal conditions revealed the kinetic relation between structurally unrelated bismuth ferrites. We report the synthetic conditions that disclose the in situ transformation of Bi25FeO39 into BiFeO3 by only extending the time for crystallization. We also demonstrate how a careful investigation of the early stages of multiferroics crystallization provides cheap and easy room-temperature access to the important sillenite-type of structure of Bi25FeO39. The crystal structure analysis by the Rietveld method and magnetization measurements provided detailed structure and magnetic relations between the synthesis conditions and the properties of the run product. The BiFeO3 antiferromagnetic behavior with a small ferromagnetic component arising from the particle's surface uncompensated spins is ascertained.

Hydrothermal synthesis of copper zirconium phosphate hydrate [Cu(OH)2Zr(HPO4)2·2H2O] and an investigation of its lubrication properties in grease.

Copper zirconium phosphate hydrate (Cu(OH)2Zr(HPO4)2·2H2O, hereafter referred to as Cu-α-ZrP) with high crystallinity was directly synthesized in a NaF-CuO-ZrO-P2O5-H2O system under hydrothermal conditions. The copper ion was confirmed to be an exchangeable cation in the Cu-α-ZrP through elemental analysis and a proton ion exchange process. The crystal structure of the Cu-α-ZrP was determined ab initio by using X-ray powder diffraction data. In the structure, the CuO6 octahedron would be located in an exchangeable atom position. Moreover, Cu-α-ZrP was evaluated as an additive in grease in a four ball test. The maximum nonseizure load (PB, representing the load-carrying capacity) of the base grease containing Cu-α-ZrP was increased from 353 to 1235 N. The excellent load-carrying capacity may be explained by the easier adherence of the material to the worn surface forming a tight protective film.

Temperature- and vacuum-induced framework contraction of Na-ETS-4.

For the first time, reduced pressure to induce a framework contraction of the microporous titanosilicate ETS-4 is used. A vacuum of 10(-2) Torr decreases the temperature of structural contraction from 200 degrees C to near room temperature and presents a potential alternative to the temperature-induced and anion-controlled molecular gate effect. The dimensions and the reversibility of the temperature- and vacuum-induced framework contractions are evaluated by in situ X-ray diffraction experiments. On the basis of these studies, it is revealed that Na-ETS-4 possesses a more rigid framework than Sr-ETS-4, which discloses a way to control the framework flexibility of ETS-4.

Heteroepitaxial growth of MFI zeolite over titanosilicate molecular sieves.

For the first time heteroepitaxial growth of MFI zeolite over ETS-4 and ETS-10 is described, and a structural model of the interface between the molecular sieves is proposed.

New crystalline layered zinc phosphate with 10-membered-ring channels perpendicular to layers.

A novel layered zinc phosphate, [N(2)C(6)H(12)](2)[Zn(7)H(3)(HPO(4-x))(5)(PO(4))(3)]H(2)O, with unique 10-membered-ring ellipsoidal channels running perpendicularly to ladder-shaped tetrahedral layers, has been synthesized ionothermally via in situ generation of 1,4-diazabicyclo[2.2.2]octane.

Hydrothermal synthesis, crystal structure, and magnetic properties of a new inorganic vanadium(III) phosphate with a chain structure.

A new vanadium(III) phosphate, Na3V(OH)(HPO4)(PO4), has been synthesized by using mild hydrothermal conditions under autogeneous pressure. This material represents a very rare example of sodium vanadium(III) phosphate with a chain structure. The crystal structure has been determined by refinement of powder X-ray diffraction data, starting from the atomic coordinates of an isotypic compound, Na3Al(OH)(HPO4)(PO4), which was obtained under high temperature and high pressure. The phase crystallizes in monoclinic space group C2/m (No. 12) with lattice parameters a = 15.423(9) A, b = 7.280(0) A, c = 7.070(9) A, beta = 96.79(7) degrees, V = 788.3(9) A(3), and Z = 4. The structure consists of one-dimensional chains composed of corner-sharing VO5(OH) octahedra running along the b direction. They are decorated by isolated PO4 and HPO4 tetrahedra sharing two of their corners with the ones of the vanadium octahedra. The interconnection between the chains is assured by three crystallographically distinct Na(+) cations. Magnetic investigation confirms the 3+ oxidation state of the vanadium ions and reveals an antiferromagnetic arrangement between those ions through the chain.

A rapid method of synthesizing the layered titanosilicate JDF-L1.

A rapid procedure for synthesis of highly crystalline and pure samples of JDF-L1 without using organics are reactants or templates is described and indexation of the powder X-ray diffraction pattern of this phase is presented.