Contributions of CO 2 , O 2 , and H 2 O to the Oxidative Stability of Solid Amine Direct Air Capture Sorbents at Intermediate Temperature

Aminopolymer-based sorbents are preferred materials for extraction of CO2 from ambient air (direct air capture of CO2, or DAC) owing to their high CO2 adsorption capacity and selectivity at ultra dilute conditions. While those adsorptive properties are important, the stability of a sorbent is a key element in developing high-performing, cost-effective, and long-lasting sorbents that can be deployed at scale. Along with process upsets, environmental components such as CO2, O2, and H2O may contribute to long-term sorbent instability. As such, unraveling the complex effects of such atmospheric components on sorbent lifetime as they appear in the environment is a critical step to understanding sorbent deactivation mechanisms and designing more effective sorbents and processes. Here, PEI/Al2O3 sorbent is assessed over continuous and cyclic dry and humid conditions to determine the effect of the co-presence of CO2 and O2 on stability at an intermediate temperature of 70 °C. Thermogravimetric and elemental analysis in combination with in situ HATR-IR spectroscopy are performed to measure the extent of deactivation, elemental content, and molecular level changes in the sorbent due to deactivation. The thermal/thermogravimetric analysis results reveal that incorporating CO2 with O2 accelerates sorbent deactivation using these sorbents in dry and humid conditions compared to CO2-free air in similar conditions. In situ HATR-IR spectroscopy results of PEI deactivation under a CO2-air environment show the formation of primary amine species in higher quantity (compared to conditions without O2 or CO2), which arise due to C-N bond cleavage at the primary and secondary amine due to oxidative degradation. We hypothesize the formation of bound CO2 species such as carbamic acids catalyze C-N cleavage reactions in the oxidative degradation pathway by shuttling protons, resulting in a lower activation energy barrier for degradation, as probed by metadynamics simulations. In the cyclic experiment after 30 cycles, results show a gradual loss in stability (dry: 29%, humid: 52%) under CO¬2 containing air (0.04% CO2/21% O2 balance N2). However, the loss in capacity during cyclic studies is significantly less than continuous deactivation as expected.