In Situ Anchoring of Small-Sized Silver Nanoparticles on Porphyrinic Triazine-Based Frameworks for the Conversion of CO2 into α-Alkylidene Cyclic Carbonates with Outstanding Catalytic Activities under Ambient Conditions

The preparation of catalytic hybrid materials by introducing highly dispersed metallic nanoparticles into porous organic polymers (POPs) may be an ideal and promising strategy for integrated CO₂ capture and conversion. In terms of the carboxylative cyclization of propargyl alcohols with CO₂, the anchoring of silver nanoparticles (AgNPs) on functional POPs to fabricate efficient heterogeneous catalysts is considered to be quite intriguing but remains challenging. In the contribution, well-dispersed AgNPs were successfully anchored onto the porphyrinic triazine-based frameworks by a simple "liquid impregnation and in situ reduction" strategy. The presence of N-rich dual active sites, porphyrin and triazine, which acted as the electron donor and acceptor, respectively, offered a huge opportunity for the nucleation and growth of metal nanoparticles. Significantly, the as-prepared catalyst Ag/TPP-CTF shows excellent catalytic activity (up to 99%) toward the carboxylative cyclization of propargyl alcohols with CO₂ at room temperature, achieving record-breaking activities (TOF up to 615 h^-1 at 1 bar and 3077 h^-1 at 10 bar). Moreover, the catalyst can be easily recovered and reused at least 10 times with retention of high catalytic activity. The possible mechanism involves small-sized AgNP-mediated alkyne activation, which may promote highly efficient and green conversion of CO₂. This work paves the way for immobilizing metal nanoparticles onto functional POPs by surface structure changes for enhanced CO₂ catalysis.