Solid State Transport and Hydrogen Permeation in the System Nd5.5W1–xRexO11.25−δ

Nd 5.5 WO 11.25−δ is a mixed proton–electron conducting oxide, which shows an important mixed conductivity and stability in moist CO 2 environments. However, the H 2 fluxes obtained with this material are not high enough in order to apply them as H 2 separation membranes in industrial applications. Re 6+ cation presents similar ionic radii than W 6+ and Re 6+ can be reduced to different oxidation states under the operating conditions typical for hydrogen membrane separation. This fact leads to the improvement of the electronic conductivity and produce the generation of oxygen vacancies with the subsequent increase in the ionic conductivity. This work presents the synthesis as nanosized powders as well as the structural and electrochemical characterization of mixed conducting materials based on the system Nd 5.5 W 1– x Re x O 11.25−δ where x = 0, 0.1, 0.5 and 1. The evolution of the crystalline structure and the shrinkage behavior are studied as a function of the sintering temperature. Total conductivity in reducing and oxidizing environments is studied systematically for samples sintered at 1350 °C. The H/D isotopic effect and the hydration influence are also analyzed by means of DC-electrochemical measurements. H 2 permeation is carried out for the selected compound, Nd 5.5 W 0.5 Re 0.5 O 11.25−δ, in the range of 700–1000 °C, obtaining a peak H 2 flux value of 0.08 mL·min –1 ·cm –2 . The reduction of the Re cation in this compound under reducing conditions is investigated by TPR and XPS. Finally, the stability of this material under CO 2 -rich gas stream was evaluated by measuring H 2 permeation using a CO 2 containing atmosphere as sweep gas.