High Proton Conductivity of Magnetically Ordered 2D Oxalate-Bridged [MnIICrIII] Coordination Polymers with Irregular Topology.

Two heterometallic coordination polymers {[NH(CH3)2(C2H5)]8[Mn4Cl4Cr4(C2O4)12]}n (1) and {[NH(CH3)-(C2H5)2]8[Mn4Cl4Cr4(C2O4)12]}n (2) were obtained by slow evaporation of an aqueous solution containing the building block [A]3[Cr(C2O4)3] [A = (CH3)2(C2H5)NH+ or (CH3)(C2H5)2NH+] and MnCl2·2H2O. The isostructural compounds comprise irregular two-dimensional (2D) oxalate-bridged anionic layers [Mn4Cl4Cr4(C2O4)12]n8n- with a Shubnikov plane net fes topology designated as (4·82), interleaved by the hydrogen-bonded templating cations (CH3)2(C2H5)NH+ (1) or (CH3)(C2H5)2NH+ (2). They exhibit remarkable humidity-sensing properties and very high proton conductivity at room temperature [1.60 × 10-3 (Ω·cm)-1 at 90% relative humidity (RH) of 1 and 9.6 × 10-4 (Ω·cm)-1 at 94% RH of 2]. The layered structure facilitates the uptake of water molecules, which contributes to the enhancement of proton conductivity at high RH. The better proton transport observed in 1 compared to that in 2 can be tentatively attributed to the higher hydrophilicity of the cations (CH3)2(C2H5)NH+, which is closely related to their affinity for water molecules. The original topology of the anionic networks in both compounds leads to the development of interesting magnetic phases upon cooling. The magnetically ordered ground state can be described as the coupling of ferromagnetic spin chains in which Mn2+ and Cr3+ ions are bridged by bis(bidentate) oxalate groups into antiferromagnetic planes through monodentate-bidentate oxalate bridges in the layers, which are triggered to long-range order below temperature 4.45 K via weaker interlayer interactions.

Sodium-Ion Conductivity and Humidity-Sensing Properties of Na2O-MoO3-P2O5 Glass-Ceramics.

A series of glass-ceramics were prepared by heat-treatments of 40Na2O-30MoO3-30P2O5 (in mol%) glass in a temperature range from 380 (Tg) to 490 °C (Tc) and for 1-24 h. The prepared glass-ceramics contain from 2 to 25 wt.% of crystalline NaMoO2PO4. The sodium-ion conductivity in these materials decreases up to one order of magnitude with an increase in the degree of crystallization due to the immobilization of sodium ions in crystalline NaMoO2PO4. The transport of sodium ions in these materials occurs primarily through the dominant continuous glassy phase, and it is weakly affected by the sporadically distributed crystalline grains. However, the prepared glass-ceramics exhibit high proton conductivity in a humid atmosphere and remarkable humidity-sensing properties; this could be related to crystalline NaMoO2PO4, which provides sites for water adsorption. The glass-ceramic prepared at 450 °C for 24 h shows the best humidity-sensing performance among all samples, showing an increase in proton conductivity for more than seven orders of magnitude with the increase in relative humidity from 0% to 95%. Under a highly humid atmosphere (95% relative humidity and 25 °C), the proton conductivity of this glass-ceramic reaches 5.2 × 10-3 (Ω cm)-1. Moreover, the electrical response of these materials on the change in the relative humidity is linear and reversible in the entire range of the relative humidity, which indicates that they are novel promising candidates for application as humidity sensors.

A significant enhancement of sodium ion conductivity in phosphate glasses by addition of WO3 and MoO3: the effect of mixed conventional-conditional glass-forming oxides.

Ion conducting oxide glasses are attractive materials for application in various electrochemical devices and an understanding of the structure-transport properties relationship is crucial for their development. An interesting effect of glass structure on the dynamics of mobile ions is the mixed glass-former effect which causes a non-linear change of ionic conductivity when glass-forming oxides get gradually substituted. Here, we report a strong, positive effect of structural changes on the conductivity of sodium ions in two glass systems 40Na2O-xMoO3-(60-x)P2O5 and 40Na2O-xWO3-(60-x)P2O5; x = 0-50 mol% where a conventional glass-forming oxide (P2O5) is gradually replaced by WO3/MoO3 which are conditional ones. In both glass systems, the compositional change in DC conductivity is non-linear, with the maximal increase of four orders of magnitude in the case of WO3 and three orders of magnitude in the case of MoO3. This significant enhancement of ionic conductivity is related to the formation of mixed phosphate-tungstate and phosphate-molybdate units in the glass network. The facilitating effect of these structural units on sodium ion dynamics is also observed in the changes of the shape of frequency-dependent conductivity and in the values of typical spatial extent of diffusion of sodium ions known as the Sidebottom length.

High Electronically Conductive Tungsten Phosphate Glass-Ceramics.

High electronically conductive tungsten phosphate glass-ceramics have been prepared by the controlled crystallization of binary 60WO3-40P2O5 glass in the temperature range from 700 to 935 °C and for 1 to 24 h. The substantial increase in the conductivity for four orders of magnitude is a result of the formation of electronically conductive W2O3(PO4)2 and WO3 phases. At low crystallization temperature the dominant W2O3(PO4)2 phase is created, whereas at 935 °C for 24 h the formation of semiconducting WO3 crystallites of an average size of 80 nm enhances the conductivity to the highest value of 1.64 × 10-4 (Ω cm)-1 at 30 °C. The course of the crystallization and its impact on this exceptionally high electronic transport of binary tungsten phosphate glass-ceramics has been discussed in detail. Since such highly electronically conductive WO3-based glass-ceramics have a great potential as cathode/anode materials in solid state batteries and as electrocatalysts in fuel cells, it is of interest to provide a novel insight into the improvement of their electrical properties.