Facile self-repair of ultrathin palladium membranes

Abstract

Pd membranes can play an important role in H₂ separation and purification for the development of sustainable and renewable energies. By supporting on porous substrates, Pd layer thickness can be reduced to several micrometers, thus improving the H₂ permeance by several orders of magnitude. However, the supported thin Pd membranes are concomitant with pinhole formation due to either fabrication (e.g., electroless-plating) or thermal treatment, which exist as a remarkable challenge for its widespread applications. This study presents a novel and facile approach for self-repair of Pd membrane defects by immersing the stainless-steel supported Pd membranes in PdCl₂ solution. Three membranes were deliberately selected with a low selectivity of 152–1687 (400 ​°C, 0.1Mpa), for which disproportionation reactions between Pd²⁺ and Fe/Cr/Ni at the defect sites spontaneously occur leading to the formation of Pd particles at the exact point of defects. This self-repair process can be enhanced when applying a high pressure of 30–50 ​bar in the PdCl₂ solution for 30 ​min, by overcoming the capillary resistance and penetrating through the pinholes. Interestingly, densely distributed hillocks were observed on the membrane surface probably due to reduction of PdCl₂ under following H₂ treatment, thus increasing the H₂ permeance with a higher effective surface area. The H₂/N₂ selectivity can be improved by more than one order of magnitude (in the best case from 1687 to 8768) and a long-term stability test of 300 ​h was achieved for the repaired membranes, corroborating the application potential of this approach.