Alumina-Based Bifunctional Catalyst for Efficient CO 2 Fixation into Epoxides at Atmospheric Pressure.

The quest toward sustainability and decarbonization demands the development of methods for efficient carbon dioxide capture and utilization. The nonreductive CO 2 fixation into epoxides to prepare cyclic carbonates has gained attention in recent years. In this work, we report the development of guanidine hydrochloride-functionalized γ alumina (γ-Al 2 O 3 ), prepared using green solvents, as an efficient bifunctional catalyst for CO 2 fixation. The resulting guanidine-grafted γ-Al 2 O 3 (Al-Gh) proved to be an excellent catalyst to prepare cyclic carbonates from epoxides and CO 2 with high selectivity. The nitrogen-rich Al-Gh shows increased CO 2 adsorption capacity compared to that of γ-Al 2 O 3 . The as-prepared catalyst was able to carry out CO 2 fixation at 85 °C under atmospheric pressure in the absence of solvents and external additives (e.g., TBAI or KI). The material showed negligible loss of catalytic activity even after five cycles of catalysis. The catalyst successfully converted many epoxides into their respective cyclic carbonates under the optimized conditions. The gram-scale synthesis of commercially important styrene carbonates from styrene oxide and CO 2 using Al-Gh was also achieved. Density functional theory (DFT) calculations revealed the role of alumina in activating the epoxide. This activation facilitated the chloride ion to open the ring to react with CO 2 . The DFT studies also validated the role of alumina in stabilizing the electron-rich intermediates during the course of the reaction.