Insights into the Role of Polymer Conformation on the Cutoff Size of Carbon Molecular Sieving Membranes for Hydrogen Separation and Its Novel Pore Size Detection Technology

In this study, three polymer precursor conformations, dilute, semi-dilute, and concentrated, were used to fabricate carbon molecular sieving (CMS) membranes via a fixed carbonization protocol. The effects of the precursor conformation on the microstructure of the resultant CMS membranes were characterized by Raman analysis. Their ability to separate light gases, such as H₂/CH₄ and H₂/N₂, was assessed with a single-gas system. Additionally, a novel method was proposed to detect the cutoff size of the CMS membranes created in this study. The method combined high-resolution transmission electron microscopy (HR-TEM) and a focused ion beam (FIB) system. Finally, due to the semi-dilute solution's denser polymer chains and lack of severe polymer entanglement, highly graphited CMS membranes with excellent gas separation performance were successfully synthesized using a semi-dilute polyetherimide dope solution. Interlayer distances in the carbon matrix were visualized and measured using our novel probing tool (HR-TEM and FIB) and software. The CMS membrane fabricated with a semi-dilute dope exhibited the best gas separation performance of the tested membranes. It had the most ordered carbon sheet orientation and exhibited a superior selectivity of H₂/CH₄ = 293 with a hydrogen permeability of 1138.7 Barrer, far surpassing the reported permselectivity of other membranes. We believe that the high H₂/CH₄ selectivity presented here is unprecedented for CMS membranes reported in the literature.