Molecular Insights into Carbon Dioxide Sorption in Hydrazone-Based Covalent Organic Frameworks with Tertiary Amine Moieties

Tailorable sorption properties at the molecular level are key for efficient carbon capture and storage and a hallmark of covalent organic frameworks (COFs). Although amine functional groups are known to facilitate CO₂ uptake, atomistic insights into CO₂ sorption by COFs modified with amine-bearing functional groups are scarce. Herein, we present a detailed study of the interactions of carbon dioxide and water with two isostructural hydrazone-linked COFs with different polarities based on the 2,5-diethoxyterephthalohydrazide linker. Varying amounts of tertiary amines were introduced in the COF backbones by means of a copolymerization approach using 2,5-bis­(2-(dimethylamino)­ethoxy)­terephthalohydrazide in different amounts ranging from 25 to 100% substitution of the original DETH linker. The interactions of the frameworks with CO₂ and H₂O were comprehensively studied by means of sorption analysis, solid-state NMR spectroscopy, and quantum-chemical calculations. We show that the addition of the tertiary amine linker increases the overall CO₂ sorption capacity normalized by the surface area and of the heat of adsorption, whereas surface areas and pore size diameters decrease. The formation of ammonium bicarbonate species in the COF pores is shown to occur, revealing the contributing role of water for CO₂ uptake by amine-modified porous frameworks.