Cooperative CO(2) Absorption Isotherms from a Bifunctional Guanidine and Bifunctional Alcohol

[Image: see text] Designing new liquids for CO(2) absorption is a challenge in CO(2) removal. Here, achieving low regeneration energies while keeping high selectivity and large capacity are current challenges. Recent cooperative metal–organic frameworks have shown the potential to address many of these challenges. However, many absorbent systems and designs rely on liquid capture agents. We present herein a liquid absorption system which exhibits cooperative CO(2) absorption isotherms. Upon introduction, CO(2) uptake is initially suppressed, followed by an abrupt increase in absorption. The liquid consists of a bifunctional guanidine and bifunctional alcohol, which, when dissolved in bis(2-methoxyethyl) ether, forms a secondary viscous phase within seconds in response to increases in CO(2). The precipitation of this second viscous phase drives CO(2) absorption from the gas phase. The isotherm of the bifunctional system differs starkly from the analogous monofunctional system, which exhibits limited CO(2) uptake across the same pressure range. In our system, CO(2) absorption is strongly solvent dependent. In DMSO, both systems exhibit hyperbolic isotherms and no precipitation occurs. Subsequent (1)H NMR experiments confirmed the formation of distinct alkylcarbonate species having either one or two molecules of CO(2) bound. The solvent and structure relationships derived from these results can be used to tailor new liquid absorption systems to the conditions of a given CO(2) separation process.