Effect of B-site europium doping on the hydrogen transport properties of barium cerate.

摘要

Barium cerate doped with europium on the Ce-site (B-site of the ABO3 perovskite structure) has been investigated as a potential material for hydrogen separation. Barium cerate doped with 15 mol% europium (BaCe0.85Eu0.15O3-delta) demonstrated higher electrical conductivity in a hydrogen-containing gas stream than gadolinium-doped barium cerate (BaCe0.85Gd0.15O3-delta), which was known to have one of the highest conductivities (0.027 S/cm 2 compared to 0.021 S/cm2 at 800°C). For europium dopant levels between 5 to 25 mol%, the sample doped with 15 mol% demonstrated higher electrical conductivities in dry forming gas (4% H2/96% N2) dry air, and wet nitrogen. The activation energies in dry air (∼0.60 eV) were indicative of p-type electronic conduction, and the activation energies in hydrogen-containing gases (∼0.35--0.45 eV) were indicative of protonic conduction. With BaCe0.85Eu0.15O3-delta , the onset of n-type electronic conductivity necessary for hydrogen separation was shown to occur at ∼600°C.; A gas-tight glass seal was developed to study the hydrogen permeation properties of BaCe0.85Eu0.15O3-delta. The glass seal was a composite of a glass containing strontium oxide, boron oxide, silicon oxide, aluminum oxide, and lanthanum oxide mixed with doped barium cerate powder. The seal would form at temperatures >875°C, allowing for testing down to 650°C.; The effect of temperature, feed-side hydrogen partial pressure, and membrane thickness on hydrogen permeation flux of BaCe0.85Eu0.15O 3-delta was investigated. For the range of thicknesses studied (0.75 to 2.00 mm), the performance of BaCe0.85Eu0.15O 3-delta membranes is under mixed control of bulk diffusion and surface kinetics. This mixed control indicates that investigating BaCe 0.85Eu0.15O3-delta membranes thinner than 0.75 mm would result in a limited increase in hydrogen permeation flux unless measures were taken to improve surface kinetics. The need for improved surface kinetics was confirmed when surface modification using porous platinum on a 1.00 mm membrane resulted in an increase in permeation flux.