Kinetic Study of CeO ₂ -Catalyzed CO ₂ Cycloaddition into Propylene Carbonate

The catalytic conversion of CO2 into value-added chemicals is a key strategy for sustainable chemical production and for mitigating greenhouse gas emissions. The process offers a green alternative to traditional phosgene-based methods, achieving high selectivity and atom economy while eliminating solvent-related waste. Kinetic analysis was conducted to investigate the effects of temperature, CO2 pressure, reaction time, and catalyst loading on the reaction rate, focusing on intrinsic kinetics free from mass-transfer limitations. This study presents a quantitative kinetic analysis of CeO2-catalyzed propylene carbonate synthesis, elucidating the reaction mechanism through experimental data and Langmuir–Hinshelwood modeling. Kinetic modeling discriminates between Langmuir–Hinshelwood and Eley–Rideal mechanisms, confirming a first-order dependence on PO and CO2, with rate inhibition at high CO2 pressures due to competitive adsorption. Experimentally derived equilibrium constants align with thermodynamic predictions. Density functional theory and Born–Oppenheimer molecular dynamics validate the catalyst’s 90-atom fluorite structure and thermal stability under reaction conditions. These insights position CeO2 as a robust, recyclable option for sustainable CO2 utilization in cyclic carbonate production.