Ag Nanoparticles Anchored on Nanotubular Porous Porphyrin Networks for Carboxylative Cyclization of Propargyl Alcohols with CO2

Abstract

AbstractA nanotubular porous porphyrin‐based network (NT‐PPN) was prepared through Friedel–Crafts alkylation polyreaction of meso‐tetraphenylporphyrin iron chloride and subsequent demetalization reaction with concentrated hydrochloric acid. As a superior support, NT‐PPN was decorated with Ag nanoparticles to generate the desired catalyst (Ag@NT‐PPN). Ag@NT‐PPN had a high BET surface area with plentiful hierarchical porosity, considerable CO2 adsorption uptake, as well as high CO2/N2 adsorption selectivity. In the presence of 1,8‐diazabicyclo[5.4.0]undec‐7‐ene (DBU), Ag@NT‐PPN exhibited excellent catalytic performance for the solvent‐free synthesis of α‐alkylidene cyclic carbonates from propargyl alcohols and CO2 at 30 °C. Ag@NT‐PPN also displayed robust constancy, excellent recyclability, and acceptable substrate expansibility for this reaction. Moreover, low concentration of CO2 derived from mixed gas (15% CO2+85% N2 in volume) was positively amenable to this catalytic protocol. This work might offer an opportunity to design metal NPs‐based heterogeneous catalysts and provide a promising candidate for application in the transformation of CO2 into valuable cyclic carbonates.