Spontaneous, Catalyst‐Free Co‐Polymerization of Ionic Liquids With CO ₂ Toward Polycarbonate

The conversion of carbon dioxide (CO 2 ) into value‐added polymer is a cornerstone of sustainable chemistry, yet current strategies typically require high pressures, metal catalysts, and yield materials with limited functionality. Herein, we report a spontaneous, catalyst‐free polymerization that directly converts CO 2 and hydroxyl‐functionalized ionic liquids (ILs) into multifunctional ionic polycarbonates under ambient conditions (0.1 MPa, 60°C). Mechanism studies, combining spectroscopic analysis and density functional calculations, elucidate a synergistic process wherein IL cations function as CO 2 concentrators, while OH − anions drive the polymerization via a bicarbonate‐mediated nucleophilic pathway. This approach yields a well‐defined ionic polycarbonate that uniquely integrates high ionic conductivity (>10 − 4 S·m − 1 ), dual‐wavelength fluorescence, broad‐spectrum antibacterial activity (>99% inhibition against E. coli and S. aureus ), and performance as a multifunctional adhesive enhancer with self‐monitoring capability. Furthermore, these polymers undergo complete degradation into monomeric constituents, establishing a closed‐loop monomer‐polymer‐monomer lifecycle. This work provides a paradigm for sustainable CO 2 valorization into advanced multifunctional materials, with immediate potential in smart adhesives, wearable electronics, and information encryption.