Modified melamine-based porous organic polymers with imidazolium ionic liquids as efficient heterogeneous catalysts for CO cycloaddition.

The chemical conversion of carbon dioxide (CO) into highly value-added products not only alleviates the environmental issues caused by global warming but also makes an impact on economic benefits in the world. The synthesis of cyclic carbonates by the cycloaddition of CO with epoxides is one of the most attractive methods for CO conversion. However, the development of green and highly efficient heterogeneous catalysts is considered to be a great challenge in catalysis. In this work, alkenyl-modified melamine-based porous organic polymer (MPOP-4A) was firstly synthesized by a one-pot polycondensation method, and it was again modified with imidazolium-based ionic liquids to obtain final modified catalyst (MPOP-4A-IL). Various analytical techniques were used to confirm structure and chemical composition of the prepared materials. The MPOP-4A-IL catalyst synthesized by the post-modification strategy with imidazolium-based ionic liquids exhibited enhanced catalytic activity for CO cycloaddition reaction. The enhanced catalytic performance could be attributed to the presence of abundant active sites in their structure such as hydrogen bond donors (HBD), nitrogen (N) sites, and nucleophilic groups for an effective chemical reaction. The MPOP-4A-IL catalyst was found to be metal-free, easy to recycle and reuse, and has good versatility for a series of different epoxides. The interaction of MPOP-4A-IL catalyst with epoxide and CO was further verified by density functional theory (DFT) calculations, and the possible mechanism of the CO cycloaddition reaction was proposed.