Abstract:
Electricity production from fossil fuels and hydrogen production from steam reformation represent two single-site large scale sources of CO2. Separation of CO2 from these sources via the pre-combustion capture process delivers multiple benefits – cleaner electricity, mitigates the global CO2 concentration and generates a large stream of H2, a clean burning fuel. This requires separation of CO2 from high pressure gas mixtures, which is best achieved by pressure/temperature swing adsorption processes. The efficiency of such processes to a large extent relies on the performance of the solid sorbent. Both processes occur under steam-rich, high temperature and pressure conditions. Developing sorbents to capture CO2 under such harsh conditions is challenging and rewarding. Porous organic polymers constructed from strong covalent links are promising candidates owing to their high thermal as well as chemical stability and can be tuned to adopt a microporous structure to gain substantial molecular sieving effects. Here we report Bakelite-type porous organic polymers synthesized via catalyst-free C–C bond formation reactions. These polymers exhibit high CO2 capacity (∼15 mmol g−1 at 35 bar), selectivity (S(60H2/40CO2) = 200 and S(80H2/20CO2) = 289, both at 298 K and 10 bar) and a record-breaking working capacity (∼6.8 mmol g−1 for a 10 to 1 bar pressure swing). Additionally, these amorphous polymers show fast diffusion kinetics (Dc = ∼7.5 × 10−9 m2 s−1), comparable to highly crystalline MOFs, which explains their high CO2 capacity (2.42 to 3.52 mmol g−1) under dynamic CO2/H2 flow. The high surface hydrophobicity, basicity and polarity of these functionalized phenol-aldehyde frameworks make them most selective for CO2 capture even under chemically demanding humid conditions.