Importance of the support material in thin palladium composite membranes for steady hydrogen permeation at elevated temperatures

Hydrogen permeation performance of palladium membranes supported on porous α-alumina and yttria-stabilized zirconia (YSZ) was studied at 300–850 °C. The hydrogen permeation flux across the palladium–α-alumina membrane decreased markedly during permeation tests conducted at >600 °C. The SEM and XPS studies of the post-test membrane revealed the presence of aluminium in the palladium layer. Such migration of aluminium was not observed by heating the palladium–α-alumina membrane under an argon atmosphere, indicating that hydrogen is responsible for this phenomenon. Hydrogen-induced strong metal-support interaction might be related to this considerable loss of the hydrogen flux. Reduction of alumina to Al(0) by active hydrogen at the membrane–support interface and subsequent migration of Al(0) into the palladium layer represents the most plausible mechanism for the aluminium diffusion. Actually, Al(0) that migrated into the palladium membrane layer generated less hydrogen-permeable palladium–aluminium alloy or inter-metallic compound phase. In contrast, no such strong interaction was found between the YSZ support and the palladium membrane. This composite membrane exhibited a steady permeation of hydrogen at 650 °C for 336 h. Having a remarkably high reduction potential, Y(III) is unlikely to be reduced to Y(0), although Zr(IV) has a comparable reduction potential to that of Al(III). A binary phase diagram shows a liquid alloy phase present for the Pd/Al couple at temperatures greater than 615 °C (eutectic point), while an inter-metallic compound or liquid alloy phase in the Pd–Zr binary system is not apparent at temperatures less than 750 °C. Consequently, inter-diffusion of zirconium with palladium did not occur during operations at 650 °C.