Preparation of a Sulfur-Functionalized Microporous Polymer Sponge and In Situ Growth of Silver Nanoparticles: A Compressible Monolithic Catalyst

We report a compressible monolithic catalyst based on a microporous organic polymer (MOP) sponge. The monolithic MOP sponge was synthesized via Sonogashira-Hagihara coupling reaction between 1,4-diiodotetrafluorobenzene and 1,3,5-triethynylbenzene in a cosolvent of toluene and TEA (2:1, v/v) without stirring. The MOP sponge had an intriguing microstructure, where tubular polymer fibers having a diameter of hundreds of nanometers were entangled. It showed hierarchical porosity with a Brunauer-Emmett-Teller (BET) surface area of 512 m² g^-1. The MOP sponge was functionalized with sulfur groups by the thiol-yne reaction. The functionalized MOP sponge exhibited a higher BET surface area than the MOP sponge by 13% due to the increase in the total pore and micropore volumes. A MOP sponge-Ag heterogeneous catalyst (S-MOPS-Ag) was prepared by in situ growth of silver nanoparticles inside the sulfur-functionalized MOP sponge by the reduction of Ag⁺ ions. The catalytic activity of S-MOPS-Ag was investigated for the reduction reaction of 4-nitrophenol in an aqueous condition. When S-MOPS-Ag was compressed and released during the reaction, the rate of the reaction was considerably increased. S-MOPS-Ag was easily removed from the reaction mixture owing to its monolithic character and was reused after washing and drying.