Preparation Of Ordered N-doped Mesoporous Phenolic Resin Polymers For The Catalytic Conversion Of Carbon Dioxide Related Reactions

CO₂ is actually an abundant and non-toxic C1 resource.Conversion of CO₂ to value-added products is of great importance for green chemistry.Heterogeneous catalysts,which could be easily recycled and eco-friendly,are widely used in the fixation and conversion of CO₂.Ordered mesoporous phenolic resin materials,possessing high specific surface area,adjustable pore structure and large pore size,have been widely used as heterogeneous catalysts or catalyst carriers.Herein,series of N-doped ordered mesoporous phenolic resin materials were prepared and used for the catalytic conversion of the CO₂ related reactions.The detailed contents are as follows:1.Dimethylamino-functionalized ordered mesoporous phenolic polymers NMe₂-MPs were directly prepared via the evaporation-induced self-assembly by using 4-dimethylaminophenol,phenol,formaldehyde and F127.The prepared NMe₂-MPs were used to catalyze the reaction of o-phenylenediamine with carbon dioxide.An optimized yield of 95%could be obtained at 1 MPa and 120 ? after 12 hours.The prepared catalysts showed excellent substrate universality and recyclability.High product yield could still be obtained after five cycles.2.Mesoporous polymer supported silver nanoparticle catalysts NMe₂-MPs/Ag were prepared using the NMe₂-MPs prepared above as the carrier.The silver ions were adsorbed in-situ and reduced to silver nanoparticles.Characterizations such as XRD,TEM and XPS confirmed that the metallic silver nanoparticles were successfully loaded on NMe₂-MPs.The NMe₂-MPs/Ag exhibited excellent performance in the reaction of propargyl alcohol,carbon dioxide and primary amine,with the yield of 96%at 40°C and atmospheric pressure.No obvious decrease in the product yield could be observed after 5 catalytic cycles.3.The TBD-functionalized ordered mesoporous polymers(TBD-FDU)were prepared via the evaporation-induced self-assembly of resole,organic base TBD and template F127.The prepared materials were used to catalyze the coupling reaction of carbon dioxide,N-phenylhydrazone and pyrrolidine.Good product yield could be obtained at 120 ? and 2 MPa.TBD-FDU exhibited excellent substrate universality and recyclability,with no obvious decrease in the catalytic performance after 5 catalytic cycles.It should be mentioned that this is the first report on the reaction of carbon dioxide,N-phenylhydrazone and pyrrolidine catakyzed by the heterogeneous catalyst.