Work

H2O and CO2 Sorption in Ion-Exchange Sorbents: Distinct Interactions in Amine Versus Quaternary Ammonium Materials

Year: 2025

Type: article

Abstract: This study investigates the H2O and CO2 sorption behavior of two chemically distinct polystyrene-divinylbenzene-based ion exchange sorbents: a primary amine and a permanently charged strong base quaternary ammonium (QA+) group with (bi)carbonate counter anions. We compare their distinct interactions with H2O and CO2 through simultaneous thermal gravimetric, calorimetric, gas analysis, and molecular modeling approaches to evaluate their performance for dilute CO2 separations like direct air capture. Thermal and hybrid (heat + low-temperature hydration) desorption experiments demonstrate that the QA+-based sorbent binds both water and CO2 more strongly than the amine counterparts but undergoes degradation at moderate temperatures, limiting its compatibility with thermal swing regeneration. However, a low-temperature moisture-driven regeneration pathway is uniquely effective for the QA+-based sorbent. To inform the energetics of a moisture-based CO2 separation (i.e., a moisture swing), we compare calorimetric water sorption enthalpies to Clausius–Clapeyron-derived total isosteric enthalpies. To our knowledge, this includes the first direct calorimetric measurement of water sorption enthalpy in a QA+-based sorbent. Both methods reveal monolayer-multilayer sorption behavior for both sorbents, with the QA+-based material having slightly higher water sorption enthalpies at the initially occupied strongest sorption sites. Molecular modeling supports this observation, showing higher water sorption energies and denser charge distributions in the QA+-based sorbent at λH2O = 1 mmol/mmolsite. Mixed gas experiments in the QA+-based sorbent show that not only does water influence CO2 binding, but CO2 influences water uptake through counterion-dependent hydration states, and that moisture swing responsiveness in this material causes hydration-induced CO2 release and drying-induced CO2 uptake, an important feature for low-energy CO2 separation under ambient conditions. Overall, the two classes of sorbents offer distinct pathways for the CO2 separation.

Source: ACS Applied Materials & Interfaces

DOI: 10.1021/acsami.5c12939

Authors: Golnaz Najaf Tomaraei, Sierra Binney, Ryan Stratton, Houlong Zhuang, Jennifer L. Wade

Institutions: Northern Arizona University, Arizona State University

Language: English

Topic: Carbon Dioxide Capture Technologies

Subfield: Mechanical Engineering

Field: Engineering

Domain: Physical Sciences

SDG: Climate action

Open Access status: hybrid

Estimated APC paid: $4,500