Amine Chemistry of Porous CO₂ Adsorbents

ConspectusAs renewable energy and CO₂ utilization technologies progress to make a more significant contribution to global emissions reduction, carbon capture remains a critical component of the mission. Current CO₂ capture technologies involve operations at point sources such as fossil fuel-based power plants or source-agnostic like in direct air capture. Each strategy has its own advantages and limitations, but in common, they all employ sorption-based methods with the use of sorbents strongly adhering to CO₂. Amine solutions are the most widely used absorbents for industrial operations due to the robust chemical bonds formed between amines and CO₂ under both dry and humid conditions, rendering excellent selectivity. Such strong binding, however, causes problematic regeneration. In contrast, purely physisorptive porous materials with high surface areas allow for the confinement of CO₂ inside narrow pores/channels and have a lower regeneration energy demand but with decreased selectivity and capacity. The most promising solution would then be the unification of both types of sorbents in one system, which could bring about a practical adsorption-desorption process. In other words, the development of porous solid materials with tunable amine content is necessary to leverage the high contact surface of porous sorbents with the added ability to manipulate amine incorporation toward lower CO₂ binding strength.To answer the call to uncover the most feasible amine chemistry in carbon capture, our group has devoted intense effort to the study of amine-based CO₂ adsorbents for the past decade. Oriented along practicality, we put forth a principle for the design of our materials to be produced in no more than three synthetic steps with economically viable starting materials. Porous organic polymers with amine functionalities of various substitutions, meaning primary, secondary, and tertiary amines, were synthesized and studied for CO₂ adsorption. Direct synthesis proved to be feasibly applicable for secondary and tertiary amine-incorporated porous polymers whereas primary-amine-based sorbents would be conveniently obtained via postsynthetic modifications. Sorbents based on tertiary amines exhibit purely physical adsorption behavior if the nitrogen atoms are placed adjacent to aromatic cores due to the conjugation effect that reduces the electron density of the amine. However, when such conjugation is inhibited, chemisorptive activity is observed. Secondary amine adsorbents, in turn, express a higher binding strength than tertiary amine counterparts, but both types can merit a strengthened binding by the physical impregnation of small-molecule amines. Sorbents with primary-amine tethers can be obtained via postsynthetic transformation of precursor functionalities, and for them, chemical adsorption is mainly at work. We conclude that mixed-amine systems could exhibit unprecedented binding mechanisms, resulting in exceptionally specific interactions that would be useful for the development of highly selective sorbents for CO₂.