Synthesis and characterization of nonsubstituted and substituted proton-conducting La(6-x)WO(12-y).

Mixed proton-electron conductors (MPEC) can be used as gas separation membranes to extract hydrogen from a gas stream, for example, in a power plant. From the different MPEC, the ceramic material lanthanum tungstate presents an important mixed protonic-electronic conductivity. Lanthanum tungstate La(6-x)WO(12-y) (with y = 1.5x + δ and x = 0.5-0.8) compounds were prepared with La/W ratios between 4.8 and 6.0 and sintered at temperatures between 1300 and 1500 °C in order to study the dependence of the single-phase formation region on the La/W ratio and temperature. Furthermore, compounds substituted in the La or W position were prepared. Ce, Nd, Tb, and Y were used for partial substitution at the La site, while Ir, Re, and Mo were applied for W substitution. All substituents were applied in different concentrations. The electrical conductivity of nonsubstituted La(6-x)WO(12-y) and for all substituted La(6-x)WO(12-y) compounds was measured in the temperature range of 400-900 °C in wet (2.5% H2O) and dry mixtures of 4% H2 in Ar. The greatest improvement in the electrical characteristics was found in the case of 20 mol % substitution with both Re and Mo. After treatment in 100% H2 at 800 °C, the compounds remained unchanged as confirmed with XRD, Raman, and SEM.

Unravelling the crystal structure of Nd5.8WO12-δ and Nd5.7W0.75Mo0.25O12-δ mixed ionic electronic conductors.

Mixed ionic electronic conducting ceramics Nd6-y WO12-δ (δ is the oxygen deficiency) provide excellent stability in harsh environments containing strongly reactive gases such as CO2, CO, H2, H2O or H2S. Due to this chemical stability, they are promising and cost-efficient candidate materials for gas separation, catalytic membrane reactors and protonic ceramic fuel cell technologies. As in La6-y WO12-δ, the ionic/electronic transport mechanism in Nd6-y WO12-δ is expected to be largely controlled by the crystal structure, the conclusive determination of which is still lacking. This work presents a crystallographic study of Nd5.8WO12-δ and molybdenum-substituted Nd5.7W0.75Mo0.25O12-δ prepared by the citrate complexation route. High-resolution synchrotron and neutron powder diffraction data were used in combined Rietveld refinements to unravel the crystal structure of Nd5.8WO12-δ and Nd5.7W0.75Mo0.25O12-δ. Both investigated samples crystallize in a defect fluorite crystal structure with space group Fm 3 m and doubled unit-cell parameter due to cation ordering. Mo replaces W at both Wyckoff sites 4a and 48h and is evenly distributed, in contrast with La6-y WO12-δ. X-ray absorption spectroscopy as a function of partial pressure pO2 in the near-edge regions excludes oxidation state changes of Nd (Nd3+) and W (W6+) in reducing conditions: the enhanced hydrogen permeation, i.e. ambipolar conduction, observed in Mo-substituted Nd6-y WO12-δ is therefore explained by the higher Mo reducibility and the creation of additional - disordered - oxygen vacancies.

Enhanced H2 separation through mixed proton-electron conducting membranes based on La5.5 W0.8 M0.2 O11.25-δ.

La(5.5) WO11.25-δ is a proton-conducting oxide that shows high protonic conductivity, sufficient electronic conductivity, and stability in moist CO2 environments. However, the H2 flows achieved to date when using La(5.5) WO11.25-δ membranes are still below the threshold for practical application in industrial processes. With the aim of improving the H2 flow obtained with this material, La(5.5) WO11.25-δ was doped in the W position by using Re and Mo; the chosen stoichiometry was La(5.5) W0.8 M0.2 O11.25-δ . This work presents the electrochemical characterization of these two compounds under reducing conditions, the H2 separation properties, as well as the influence of the H2 concentration in the feed stream, degree of humidification, and operating temperature. Doping with both Re and Mo enabled the magnitude of H2 permeation to be enhanced, reaching unrivaled values of up to 0.095 mL min(-1) cm(-2) at 700 °C for a La(5.5) W0.8 Re0.2 O11.25-δ membrane (760 µm thick). The spent membranes were investigated by using XRD, SEM, and TEM on focused-ion beam lamellas. Furthermore, the stability in CO2 -rich and H2 S-containing atmospheres was evaluated, and the compounds were shown to be stable in the atmospheres studied.