Branched versus Linear Structure: Lowering the CO₂ Desorption Temperature of Polyethylenimine-Functionalized Silica Adsorbents

Lowering the regeneration temperature for solid CO2-capture materials is one of the critical tasks for economizing CO2-capturing processes. Based on reported pKa values and nucleophilicity, we compared two different polyethylenimines (PEIs): branched PEI (BPEI) and linear PEI (LPEI). LPEI outperformed BPEI in terms of adsorption and desorption properties. Because LPEI is a solid below 73–75 °C, even a high loading amount of LPEI can effectively adsorb CO2 without diffusive barriers. Temperature-programmed desorption (TPD) demonstrated that the desorption peak top dropped to 50.8 °C for LPEI, compared to 78.0 °C for BPEI. We also revisited the classical adsorption model of CO2 on secondary amines by using in situ modulation excitation IR spectroscopy, and proposed a new adsorption configuration, R1(R2)-NCOOH. Even though LPEI is more expensive than BPEI, considering the long-term operation of a CO2-capturing system, the low regeneration temperature makes LPEI attractive for industrial applications