Lysine Anion‐Functionalized Swelling Poly(Ionic Liquid)s as Efficient Catalysts for CO₂‐Assisted Epoxide Hydrolysis at Atmospheric Pressure

CO 2 ‐assisted indirect hydrolysis of epoxides is a common method for producing 1,2‐diols but suffers from high CO 2 pressure. Herein, a novel lysine anion‐functionalized swelling poly(ionic liquid) ([Am‐SPILs]Lys) is efficiently applied as the catalyst for CO 2 ‐assisted epoxide hydrolysis at atmospheric pressure. The product yield demonstrates a positive correlation with the catalyst's swelling capacity, tunable by adjusting the crosslinker content. When the crosslinker mass constitutes 20% of the ionic liquid monomer, [Am‐SPILs]Lys exhibits exceptional catalytic activity, achieving 98.67% conversion and 95.68% selectivity. Moreover, over five reuse cycles, [Am‐SPILs]Lys maintains high and stable activity without notable catalytic performance degradation. This remarkable performance is attributed to the high swelling ability of [Am‐SPILs]Lys, facilitating solvent penetration and complete exposure of active sites, thereby creating a quasi‐homogeneous catalytic environment. The aminoimidazole and lysine anions in [Am‐SPILs]Lys serve as hydrogen bond donors and alkaline sites, continuously activating reactants and stabilizing intermediates, thus enhancing catalytic activity. The Lewis base amine group of the nitrogen‐rich unit can activate CO 2 through carbamate formation, overcoming the reaction inertia and enabling the process under atmospheric conditions. This strategy leads to an environmentally friendly catalyst for the synthesis of 1,2‐diols using atmospheric CO 2 , with potential applications in energy and chemical engineering.