Four new compounds containing vanadosilicate clusters have been synthesized by hydrothermal reactions. The clusters are derived from the [V18O42] Keggin cluster by substitution of V=O caps by Si2O(O,OH)2 species. In Cs9[(V15Si6O46(OH)2Cl)(V2O4)](H2O)6.2, 1, the [V15Si6O46(OH)2] cluster shells are covalently interconnected by VO4 tetrahedra to form an infinite layer. In ((CH3)4N)4[V15Si6O42(OH)6(H2O)](H2O)20, 2, and ((CH3)4N)4(V(H2O)6)2/3 [V15Si6O42(OH)6 (H2O)](H2O), 3, separated [V15Si6O42(OH)6] cluster shells are interlinked by hydrogen bonds to form frameworks with wide channel systems. The separated cluster shell in ((CH3)4N)4((CH3)2NH2)((CH3)2NH) [V14Si8O42(OH)8(HCO2)] (H2O)4.7, 4, has four Si2O(OH)2 species in a tetrahedral configuration. The 2D structure of 1 and 0D structures of 2-4 complement the known 1D and 3D structures formed from such vanadosilicate shells.

The segregated vacancies in the A site-ordered oxygen-deficient double perovskites REBaCo2O5+x (RE = La, Pr, Nd, Sm, Eu) (RBCO) are thought to greatly enhance the diffusivity of oxide ions in the bulk of these materials and possibly supply surface defect sites with enhanced reactivity towards molecular oxygen. Some materials in this family of REBaCo2O5+x compounds, such as PrBaCo2O5+x, (PBCO), have already demonstrated high electronic conductivity, rapid oxygen ion diffusion and surface exchange kinetics. Therefore, the family of REBaCo2O5+x compounds were synthesized and evaluated as cathode materials for intermediate temperature solid oxide fuel cells (SOFCs) based on gadolinium doped ceria (CGO) electrolytes. The electrochemical performance of symmetrical cells (REBaCo2O5+x + CGO composite cathodes on the CGO electrolytes) was evaluated by using AC impedance spectroscopy. The area specific resistance (ASR) performance was measured as a function of temperature as well as oxygen partial pressure.

The electrochemical properties of perovskite-type materials, Ln2NiO4+δ (Ln = La, Pr) as cathodes on Ce0.9Gd0.1O3 (CGO) and YSZ electrolytes were studied from 400 to 700 °C under different oxygen partial pressures (pO2 = 0.01-1 atm) by using AC impedance spectroscopy. These oxide electrodes yielded lower area specific resistance (ASR) compared to manganite perovskites. Ln2NiO4+δ (Ln = La, Pr) on CGO showed similar electrochemical performance though La2NiO4 (LNO) has a smaller ASR than Pr2NiO4 (PNO). The polarization resistance of LNO on YSZ was 2 orders higher than that on CGO. The interfacial resistance between the electrode and electrolyte was much smaller for LNO on CGO than for LNO on YSZ.

Four open-framework copper titanosilicates have been synthesized by hydrothermal techniques. The crystal structure of Phase 1 determined from single crystal X-ray data is closely similar to that reported for the titanosilicate ETS-4 with ca. one third TiO5 pyramids randomly replaced by CuO4 squares. Phase 2 also has the ETS-4 structure but all the TiO5 pyramids are replaced by CuO4 squares which are not randomly disordered. Phase 3 with the composition Na8CuTi3Si16O43 has the same structure as the mineral narsarsukite, a titanosilicate closely related to the microporous titanosilicate ETS-10. Narsarsukite and ETS-10 have the same straight single chains of TiO6 octahedra which are partially substituted by CuO4 squares in 3. Phase 4 with the composition K4CuTiSi8O21 contains CuO4 squares and TiO5 tetragonal pyramids that crosslink a new type of silicate double layer to form an open framework.

Single crystals of a novel organic-inorganic framework [Fe0.28V0.72OH0.8(NH4)0.2(C8H4O4)] · 0.53(C8H6O4), 1, have been prepared by hydrothermal synthesis in the presence of an oxidizing agent. The structure was solved by single crystal X-ray diffraction: space group Pnma, a = 17.6956 (19) Å, b = 6.8745 (7) Å, c = 11.9303(12) Å. The three dimensional framework is constructed from Fe/V-O chains that are cross-linked by 1,4-benzene dicarboxylate (BDC) anions forming large one-dimensional channels. As synthesized, the compound contains additional dicarboxylate groups occupying disordered positions in the channels that can be removed by heating. The chemical reactivity of 1 and its magnetic properties are reported. The new phase is closely related to analogous Cr (III) and V(III) phases recently reported by Férey and co-workers.

A family of microporous and open-framework microporous transition metal silicates have been prepared by hydrothermal synthesis at T ≤ 240 °C. The structures of the compound are based on a common principle in which anionic silicate components (layers, chains, or cluster anions) are connected by isolated transition metal polyhedra by sharing four corners in a square arrangement. Known examples of this class of compounds are reviewed and some recent progress on extending the syntheses to include organic templates are discussed.

Ruthenium sulfide samples were prepared by flowing pure hydrogen sulfide into an aqueous solution of ruthenium chloride followed by further sulfidation in hydrogen sulfide. The final products were characterized by X-ray diffraction and crystallite-sizes were estimated from line broadening. The specific surface areas of catalysts were measured using the multipoint BET method and compositions were determined by thermogravimetric analysis. Ruthenium sulfide loaded gas diffusion electrodes were fabricated by a spraying technique and their electrochemical behavior studied. The electrochemical oxidation of hydrogen was investigated in a three -electrode cell using a ruthenium sulfide loaded gas diffusion electrode as the working electrode with humidified hydrogen containing small amounts of carbon monoxide. Results on the activity and the effects of carbon monoxide with reference to a standard platinum electrode measured at the same conditions show that ruthenium sulfide has a lower activity for hydrogen oxidation but is not susceptible to CO poisoning.

Experimental results from electrical conductivity relaxation (ECR) measurements on SrFeO3-x are described. Values of Dchem and kchem were obtained by monitoring the variation of the time dependence of the electrical conductivity after an abrupt change in the oxygen partial pressure. Values for the oxygen ion and vacancy diffusion coefficients were calculated from the measured thermodynamic factors and compared with those of other compositions in the series La1-xSrxFeO3-x. The surface exchange coefficients, kchem and kex were also determined.

The compound (H3O)1.5{[VO(H2O)]PO4}3·2.5H2O is a new member of a series of vanadium phosphates containing vanadium in both plus four and five oxidation states. Charge ordering occurs in these mixed vanadium phosphate layered compounds forming striped phases with different periodicities. The VOPO4 layers undulate as a consequence of differences in the O-O atom distances in the ordered V(V)O6 and V(IV)O6 octahedra.

The synthesis temperature for silicalite-I (MFI) can be raised to 300°C by applying high pressure to stabilize the structure-directing organic template. The elevated temperature and pressure favor theformation of crystals with improved quality. Prismatic silicalite-I crystals with a uniform size of about 0.7× 0.2 × 0.2 mm have been obtained by heating a gel prepared from TMA-silicate solution, TPABr andsodium hexafluorosilicate at 250°C under a pressure of 80 MPa. The influence of synthesis conditions on the crystal sizes has been studied by systematically changing temperature, pressure and gel compositions. Underthe specific conditions of 250°C and 80 MPa, a strong correlation was found between the crystal size andthe F/Si mole ratio of the starting gel, which enables the preparation of uniform crystals of silicalite-I with preset dimensions.

Rhombohedral (R) phases of the binary systems AE-Bi-O (AE = Ca, Sr, Ba) have low temperature (β2) and high temperature (β1) polymorphs and the β1 polymorph is a good oxygen ion conductor. In a previous study, we showed that in the ternary system Ba-Sr-Bi-O, conductivities of polycrystalline R samples are unaffected by Ba:Sr, whereas temperature ranges of the β2↔β1 polymorphic transition are. Recently, we proved that the conductivity of both polycrystalline and single-crystal R samples is sensitive to spatial direction. For single crystals, the conductivity is highest perpendicular to the c-axis. Along the conduction plane, the conductivities are significantly higher than those of polycrystalline R samples; perpendicular to that plane they are significantly lower. The BaBiO3 perovskite (P) phase, predominantly an electronic conductor, has conductivities of 10 to 102 S/cm at 350-800°C in air. Conductivity measurements of the R-P assemblages with different R:P showed that percolation threshold is around 35 volume % P.

Oxygen permeation through a new perovskite La0.5Sr0.5Fe0.8Ga0.2O3−δ membrane has been measured both under small (air/He) and large (air/CO, CO2) oxygen partial pressure gradients. In both cases oxygen transport is close to surface limited. By modeling the pressure dependence of the oxygen flow rate under small pressure gradient an ambipolar diffusion coefficient 9.65 × 10−7cm2/s and a surface exchange coefficient 7.15 × 10−6 cm/s at 974 °C were determined. With air/CO, CO2 on the permeate side, the permeability increases linearly with the partial pressure of CO. The observed increase is greater than the maximum enhancement predicted by our model.

LSCGO (La0.5Sr0.5Co0.2Ga0.2O3−δ) was selected and synthesized as a cathode material for gallate-based solid oxide fuel cells (SOFC). In the present paper, the electrode polarization behavior of LSCGO was studied under various pO2 and temperature conditions by a two-probe ac impedance method. A symmetric electrochemical cell: pO2, LSCGOILSGMOILSCGO, pO2, where the composition of the electrolyte LSGMO is La0.8Sr0.2Ga0.85Mg0.15O3−δ, was used in the study. Below 600°C, only semicircles due to bulk and grain boundary contributions were observed. In temperature range 700-800°C, however, a depressed and asymmetric semicircle was found in the low frequency regime (1 mHz to 1000 Hz). This low frequency feature in the impedance spectra is attributed to the electrode polarization process and can be fitted to the well-known Gerischer impedance equation. The resulting fitting parameters are used to derive surface exchange and bulk diffusion coefficients.

Ferroelectric SrBi2Ta2O9 (SBT) films were prepared by the spin coating technique on platinum, quartz and YBa2Cu3O7-x/LaA1O3 substrates from a methoxyethanol solution of bismuth isopropoxide (Bi(OCH(CH3)2)3) and strontium tantalum isopropoxide (SrTa2(OCH(CH3)2)12). X-Ray diffraction studies showed some crystallization occurred after annealing the films under oxygen flow at 600 °C and excellent crystallinity was achieved after annealing at 750 °C for 0.5 h. Electron microprobe analysis gave a composition close to that expected for SBT, and atomic force microscopy gave a root mean square surface roughness of 101 A. An hysteresis measurement (1 kHz) gave remnant polarization (2Pr), saturation polarization (Ps) and coercive field (Ec) values of 14.5 μC/cm2, 14.5 μ/cm2 and 59 kV/cm, respectively.

The electrocatalytic behavior of the mixed electron - ion conductor SrCo0.8Fe0.2O3-δ, in the form of an electrode on YSZ, has been studied using impedance spectroscopy at low frequencies. The results suggest that the electrode process is dominated by the surface exchange at high temperatures and by the bulk oxygen diffusion at lower temperatures. No limiting current was observed in I-V measurements. The electrode polarization decreased with increasing current density. The creation of additonal oxygen vacancies in the electrode material is suggested to account for the better performance at the higher current densities.

The blocking electrode method commonly used for the determination of the partial conductivities in a mixed ionic-electronic conductor has been suspected by several authors to give incorrect results in some cases. Experimental evidence illustrating the limitations of this method are presented. The resistance of three pellets of YSZ, the middle one playing the role of a “mixed” conductor, was studied by ac impedance spectroscopy. The imperfect contacts on a microscopic scale formed at the interface between the blocking electrodes and the sample were shown to give rise to additional resistances which cannot be separated from the total bulk resistance. The method was also used to study the conductivity of gold metal. Despite the presence of the ionically blocking electrodes an electronic current is observed. This electronic leakage current is due to the interaction with the gaseous environment, the mixed conductor playing the role of an electrode for the conversion of oxygen ions to electrons.