An ionic liquid in Core-shell structure: Halogen-free, metal-free bifunctional catalyst for olefin epoxidation and CO2 cycloaddition

We synthesized a core-shell resin structure with abundant architecture and excellent thermal stability through polymerization. Imidazole ionic liquid with varying carbon chain lengths was immobilized on the surface, resulting in the preparation of metal-free, halogen-free core-shell catalysts with different carbon chain lengths via HCO 3 - exchange. Characterization using FT-IR, XPS, and various techniques revealed the exceptional performance of our synthetic catalyst in terms of its internal structure. After extensive experimentation, we discovered that the synthesized catalyst exhibits dual functionality for epoxidation and CO 2 cycloaddition reactions without requiring solvents or co-catalysts. The epoxidation system demonstrated remarkable conversion rates and selectivity while also exhibiting strong recyclability in heterogeneous reactions, according to kinetic parameters, the reaction order of styrene, TBHP and catalyst during epoxidation is approximately 1, the reference factor for this reaction was calculated to be 6.7×10 9 (L 2 ·mol −2 ·min −1 ), with an activation energy of 48.9 kJ/mol obtained from analyzing reaction rates at different temperatures. In the CO 2 cycloaddition reaction, our catalyst exhibited an advantage in catalyzing ring-opening reactions, achieving a conversion rate of 95 % for styrene oxide within six hours along with over 99 % selectivity towards cyclic carbonate formation. It is suggested that the epoxide reaction is carried out in steps, and it is inferred that the catalyst PS-ImC 4 HCO 3 and TBHP are produced into peroxy intermediate active species TBA and HCO 4 , and the reaction between HCO 4 - and styrene is the determination step of the total reaction. The reaction rate constant k=0.009 of the absolute step is calculated based on the global optimization algorithm • A novel imidazole catalyst with core-shell structure without metal and halogen was prepared. • The heterogeneous reactions of epoxidation and CO 2 cycloaddition require no solvent, and the catalytic efficiency is high, the catalyst is easy to recover and the performance is stable. • The stepwise reaction rate constant was calculated by global optimization algorithm, and the stepwise reaction mechanism was verified.