Selective CO₂ Sequestration with Monolithic Bimodal Micro/Macroporous Carbon Aerogels Derived from Stepwise Pyrolytic Decomposition of Polyamide-Polyimide-Polyurea Random Copolymers

Polymeric aerogels (PA-XX) were synthesized via room-temperature reaction of an aromatic triisocyanate (tris(4-isocyanatophenyl) methane) with pyromellitic acid. Using solid-state CPMAS 13C and 15N NMR, it was found that the skeletal framework of PA-XX was a statistical copolymer of polyamide, polyurea, polyimide, and of the primary condensation product of the two reactants, a carbamic-anhydride adduct. Stepwise pyrolytic decomposition of those components yielded carbon aerogels with both open and closed microporosity. The open micropore surface area increased from \u3c15 m2 g-1 in PA-XX to 340 m2 g-1 in the carbons. Next, reactive etching at 1,000 °C with CO2 opened access to the closed pores and the micropore area increased by almost 4x to 1150 m2 g-1 (out of 1750 m2 g-1 of a total BET surface area). At 0 °C, etched carbon aerogels demonstrated a good balance of adsorption capacity for CO2 (up to 4.9 mmol g-1), and selectivity toward other gases (via Henry\u27s law). The selectivity for CO2 versus H2 (up to 928:1) is suitable for precombustion fuel purification. Relevant to postcombustion CO2 capture and sequestration (CCS), the selectivity for CO2 versus N2 was in the 17:1 to 31:1 range. In addition to typical factors involved in gas sorption (kinetic diameters, quadrupole moments and polarizabilities of the adsorbates), it is also suggested that CO2 is preferentially engaged by surface pyridinic and pyridonic N on carbon (identified with XPS) in an energy-neutral surface reaction. Relatively high uptake of CH4 (2.16 mmol g-1 at 0 °C/1 bar) was attributed to its low polarizability, and that finding paves the way for further studies on adsorption of higher (i.e., more polarizable) hydrocarbons. Overall, high CO2 selectivities, in combination with attractive CO2 adsorption capacities, low monomer cost, and the innate physicochemical stability of carbon render the materials of this study reasonable candidates for further practical consideration