Tetrameric self-assembling of water-lean solvents enables carbamate anhydride-based CO2 capture chemistry

• Published in: Nature chemistry 2024-07, Vol.16 (7), p.1160-1168
• Main Authors: Leclaire, Julien, Heldebrant, David J., Grubel, Katarzyna, Septavaux, Jean, Hennebelle, Marc, Walter, Eric, Chen, Ying, Bañuelos, Jose Leobardo, Zhang, Difan, Nguyen, Manh-Thuong, Ray, Debmalya, Allec, Sarah I., Malhotra, Deepika, Joo, Wontae, King, Jaelynne
• Format: Article
• Language: English
• Subjects: 639/638/224/685; 639/638/541/966; Adducts; Analytical Chemistry; Anhydrides; Biochemistry; Carbamates (tradename); Carbon dioxide; Carbon sequestration; Chemistry; Chemistry and Materials Science; Chemistry/Food Science; Clean technology; Climate change; Climate change mitigation; Clusters; Enzyme activity; Hydrogen bonding; Inorganic Chemistry; INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Micelles; Oligomerization; Organic Chemistry; Physical Chemistry; Self-assembly; Solvents; Storage capacity; sustainability
• ISSN: 1755-4330; 1755-4349; 1755-4349
• DOI: 10.1038/s41557-024-01495-z

Carbon capture, utilization and storage is a key yet cost-intensive technology for the fight against climate change. Single-component water-lean solvents have emerged as promising materials for post-combustion CO 2 capture, but little is known regarding their mechanism of action. Here we present a combined experimental and modelling study of single-component water-lean solvents, and we find that CO 2 capture is accompanied by the self-assembly of reverse-micelle-like tetrameric clusters in solution. This spontaneous aggregation leads to stepwise cooperative capture phenomena with highly contrasting mechanistic and thermodynamic features. The emergence of well-defined supramolecular architectures displaying a hydrogen-bonded internal core, reminiscent of enzymatic active sites, enables the formation of CO 2 -containing molecular species such as carbamic acid, carbamic anhydride and alkoxy carbamic anhydrides. This system extends the scope of adducts and mechanisms observed during carbon capture. It opens the way to materials with a higher CO 2 storage capacity and provides a means for carbamates to potentially act as initiators for future oligomerization or polymerization of CO 2 . Carbon capture, utilization and storage is key for climate change mitigation and developing more environmentally friendly technologies. Now it has been shown that CO 2 capture in single-component water-lean solvents is accompanied by the self-assembly of reverse-micelle-like tetrameric clusters in solution that enable the formation of various CO 2 -containing compounds.