Nitrogen-Rich Porous Organic Polymers with Supported Ag Nanoparticles for Efficient CO₂ Conversion

As CO₂ emissions increase and the global climate deteriorates, converting CO₂ into valuable chemicals has become a topic of wide concern. The development of multifunctional catalysts for efficient CO₂ conversion remains a major challenge. Herein, two porous organic polymers (NPOPs) functionalized with covalent triazine and triazole N-heterocycles are synthesized through the copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) reaction. The NPOPs have an abundant microporous content and high specific surface area, which confer them excellent CO₂ affinities with a CO₂ adsorption capacity of 84.0 mg g^-1 and 63.7 mg g^-1, respectively, at 273 K and 0.1 MPa. After wet impregnation and in situ reductions, Ag nanoparticles were supported in the NPOPs to obtain Ag@NPOPs with high dispersion and small particle size. The Ag@NPOPs were applied to high-value conversion reactions of CO₂ with propargylic amines and terminal alkynes under mild reaction conditions. The carboxylative cyclization transformation of propargylic amine into 2-oxazolidinone and the carboxylation transformation of terminal alkynes into phenylpropiolic acid had the highest TOF values of 1125.1 and 90.9 h^-1, respectively. The Ag@NPOP-1 was recycled and used five times without any significant decrease in catalytic activity, showing excellent catalytic stability and durability.