Transformation of CO₂ with Glycerol to Glycerol Carbonate over ETS-10 Zeolite-Based Catalyst

Catalytic conversion of CO₂ with the surplus glycerol (GL) produced from biodiesel manufacturing has attracted much academic and industrial attention, which proves the urgent requirement for developing high-performance catalysts to afford significant environmental benefits. Herein, titanosilicate ETS-10 zeolite-based catalysts with active metal species introduced by impregnation were employed for coupling CO₂ with GL to efficiently synthesize glycerol carbonate (GC). The catalytic GL conversion at 170 °C miraculously reached 35.0% and a 12.7% yield of GC was obtained on Co/ETS-10 with CH₃CN as a dehydrating agent. For comparison, Zn/ETS- Cu/ETS-10, Ni/ETS-10, Zr/ETS-10, Ce/ETS-10, and Fe/ETS-10 were also prepared, which showed inferior coordination between GL conversion and GC selectivity. Comprehensive analysis revealed that the presence of moderate basic sites for CO₂ adsorption-activation played a crucial role in regulating catalytic activity. Moreover, the appropriate interaction between cobalt species and ETS-10 zeolite was also of great significance for improving the glycerol activation capacity. A plausible mechanism was proposed for the synthesis of GC from GL and CO₂ in the presence of CH₃CN solvent over Co/ETS-10 catalyst. Moreover, the recyclability of Co/ETS-10 was also measured and it proved to be recycled at least eight times with less than 3% decline in GL conversion and GC yield after a simple regeneration process through calcination at 450 °C for 5 h in air.