PNNL

Abstract

Carbon capture, utilization, and storage is a key yet cost-intensive technology for the fight against climate change. In a combined experimental and modelling study of single-component water-lean solvent, we found that CO2 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 kinetic and thermodynamic features. The emergence of well-defined supramolecular architectures displaying a H-bonded internal core, reminiscent of enzymatic active sites, enables the formation of unprecedented CO2-containing molecular species such as carbamic acid, carbamic-anhydride, and alkoxy carbamic anhydrides. This dynamic combinatorial system based on a single absorbent and CO2 extends the scope of adducts and mechanisms observed during carbon capture. It opens the way to new materials with a higher CO2 storage capacity as well as provides a means for carbamates to potentially act as initiators for future oligomerization or polymerization of CO2.