Low chemical-expansion and self-catalytic nickel-substituted strontium cobaltite perovskite four-channel hollow fibre membrane for partial oxidation of methane

In membrane reactors, the thermo-mechanical stability of the membrane determines the operability of the reaction, while the permeability and catalytic performance dictate the reaction process. A high chemical expansion coefficient can exacerbate the mismatch in the thermal expansion behaviour between the two sides of the membrane, potentially resulting in fracture. The low permeability and slow catalytic activity can slow the reaction process and result in an unsatisfactory product composition. Here, a Ba_0.5Sr_0.5Co_0.7Fe_0.2Ni_0.1O_3-δ (BSCFN) four-channel hollow fibre membrane with a low chemical-expansion and high oxygen permeation flux has been successfully fabricated by phase inversion and a one-step thermal process (OSTP). Reaction sintering during the OSTP forms an NiO in-situ exsolution phase on the membrane surface, and A-site stoichiometry excess occurs, improves the oxygen permeation flux, and provides the membrane with self-catalytic ability during the partial oxidation of methane (POM) reactions. Consequently, the BSCFN membrane shows excellent performance; exhibiting an oxygen flux of 11.75 mL cm⁻²·min⁻¹ at 900 °C. Furthermore, the self-catalytic BSCFN membrane has a good hydrogen production of 10.1 mL cm⁻²·min⁻¹ during the POM process, which is 7.5 times higher than that of Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3-δ membranes (1.87 mL cm⁻²·min⁻¹). This offers a viable strategy for the development of membrane reactor applications.