Porous Organic Polymers Catalyzed by Selenides: Recognition of Selenide-Induced Oxidative Coupling and Promoting Synergistic Hydrogenation of Nitroarenes with Pd Loading

In this article, we present the first instance of selenide-induced oxidation polymerization for the construction of porous organic polymers (POPs). This method transforms common methyl aromatics into 7 series of 42 selenide-doped POPs (SePOPs) with a high surface area (up to 1636 m2 g–1). Thanks to the self-regenerable mechanism originating from the selenide-induced rapid oxygen transfer process, a low catalyst dosage (0.5 equiv) and good synthetic efficiency (near quantitative yield in 5 h) have been realized. Here, selenides serve as oxidative catalysts, porogens, and dopants simultaneously, enhancing SePOPs with abundant microporosity, ample active site exposure, and effective synergy with postloading Pd NPs. Eventually, remarkable hydrogeneration performances of nitrobenzene (99% conversion in 3 min, rt) are acquired with the product SePOP3-M1-Pd. This work carves out a protocol to integrate universal methyl monomers into SePOPs with a great compatibility of facile preparation and abundant porosity, paving a road to balance the polymerization efficiency with monomer universality in POP architecture and shedding light on the deep potential in the heterogeneous hydrogeneration catalysis of SePOPs.