Carbon Molecular Sieve Membranes from Acenaphthenequinone-Biphenyl Polymer; Synthesis, Characterization, and Effect...

A rigid, high temperature-resistant aromatic polymer, poly(1,1'-biphenyl)-6,8a-dihydroacenaphthylene-1(2H)-one (BDA) comprising acenaphthenequinone and biphenyl was successfully synthesized by superacid catalyzed polymerization. BDA has a high decomposition temperature (T_d = 520 °C) that renders it a viable candidate for carbon molecular sieve membranes (CMSM) formation. BDA precursor pyrolysis at 600 °C (BDA-P600) leads to a carbon turbostratic structure formation with graphene-like amorphous strands in a matrix with micropores and ultramicropores, resulting in a carbon structure with higher diffusion and higher selectivity than dense BDA. When the BDA pyrolysis temperature is raised to 700 °C (BDA-P700), the average stacking number of carbon layers N increases, along with an increase in the crystallite thickness stacking L, and layer plane size L, leading to a more compact structure. Pure gas permeability coefficients P are between 3 and 5 times larger for BDA-P600 compared to the BDA precursors. On the other hand, there is a P decrease between 10 and 50% for O₂ and CO₂ between CMSM BDA-P600 and BDA-P700, while the large kinetic diameter gases N₂ and CH₄ show a large decrease in permeability of 44 and 67%, respectively. It was found that the BDA-P700 WAXD results show the emergence of a new peak at 2θ = 43.6° (2.1 Å), which effectively hinders the diffusion of gases such O₂, N₂, and CH₄. This behavior has been attributed to the formation of new micropores that become increasingly compact at higher pyrolysis temperatures. As a result, the CMSM derived from BDA precursors pyrolyzed at 700 °C (BDA-P700) show exceptional O₂/N₂ gas separation performance, significantly surpassing baseline trade-off limits.