SO₄^2–/SnO₂ Solid Superacid Granular Stacked One-Dimensional Hollow Nanofiber for a Highly Conductive Proton-Exchange Membrane

A novel sulfated tin oxide solid superacid granular stacked one-dimensional (1D) hollow nanofiber (SO42–/FSnO2) is proposed as a nanofiller in sulfonated poly(phthalazinone ether sulfone ketone) (SPPESK) to manipulate a highly conductive proton nanochannel. It has unique microstructures with an open-end hollow nanofibric morphology and grain-stacked single-layer mesoporous fiber wall, which greatly enlarge the specific surface area and aspect ratio. The diverse acid sites, that is, SO42–, Sn–OH Brönsted, and Sn4+ Lewis superacids, provide a high concentration of strong acidic proton carriers on the nanofiber surface and dynamically abundant hydrogen bonds for rapid proton transfer and interfacial interactions with −SO3H groups in the SPPESK along the 1D hollow nanofiber. As a result, long-range orientated ionic clusters are observed in the SO42–/FSnO2 incorporated membrane, leading to simultaneous enhancement of proton conductivity (226.7 mS/cm at 80 °C), mechanical stability (31.4 MPa for the hydrated membrane), fuel permeation resistance, and single-cell performance (936.5 and 147.3 mW/cm2 for H2/O2 and direct methanol fuel cells, respectively). The superior performance, as compared with that of the zero-dimensional nanoparticle-incorporated membrane, Nafion 115, and previously reported SPPESK-based membranes, suggests a great potential of elaborating superstructural 1D hollow nanofillers for highly conductive proton-exchange membranes.