Competing Kinetic Consequences of CO2 on the Oxidative Degradation of Branched Poly(ethylenimine)

Abstract

Amine-functionalized porous solid materials are effective sorbents for direct air capture (DAC) of CO2. However, they are prone to oxidative degradation in service, increasing the materials cost for widespread implementation. While the identification of oxidation products has given insights into degradation pathways, the roles of some species, like CO2 itself, remain unresolved, with conflicting information in the literature. Here, we investigate the impact of CO2 on the oxidative degradation of poly(ethylenimine)-alumina (PEI/Al2O3) sorbents under conditions encompassing a wide range of CO2-air mixture compositions and temperatures relevant to DAC conditions, thereby reconciling the conflicting data in the literature. Degradation profiles characterized by thermogravimetric analysis, in situ ATR-FTIR, and CO2 capacity measurements reveal nonmonotonic effects of CO2 concentrations and temperatures on oxidation kinetics. Specifically, 0.04% CO2 accelerates PEI/Al2O3 oxidation more at low temperatures (<90 °C) compared to 1% and 5% CO2, but this trend reverses at high temperatures (>90 °C). First-principles metadynamics, machine learning accelerated molecular dynamics simulations, and 1H relaxometry experiments show that chemisorbed CO2 acid-catalyzes critical oxidation reactions, while extensive CO2 uptake reduces PEI branch mobility, slowing radical propagation. These contrasting kinetic effects of CO2 explain the complex degradation profiles observed in this work and in prior literature. Collectively, this work highlights the importance of considering atmospheric components in the design of DAC sorbents and processes. Additionally, it identifies the unconstrained branch mobility and local acid environment as two of the major culprits in the oxidation of amine-based sorbents, suggesting potential strategies to mitigate sorbent degradation.