Fe-doped H3PMo12O40 immobilized on covalent organic frameworks (Fe/PMA@COFs): a heterogeneous catalyst for the epoxidation of cyclooctene with H2O2

Abstract

Covalent organic frameworks (COFs) have arisen as one kind of devisable porous organic polymer that has attracted immense attention in catalytic applications. In this work, we prepared cost-effective imine-based COFs (COF-300, COF-LZU1 and CIN-1) via a reaction kettle operated in place of a traditional sealed Pyrex tube. Then, phosphomolybdic acid (PMA) and iron ions were immobilized on the COF supports by impregnation; the resulting frameworks were denoted as Fe/PMA@COFs (Fe/PMA@COF-LZU1, Fe/PMA@CIN-1 and Fe/PMA@COF-300). A series of characterization results demonstrated that the PMA and iron ions were uniformly dispersed on the surface/cavities of the COFs. The catalytic properties of the obtained Fe/PMA@COFs were investigated in the epoxidation of cyclooctene with H₂O₂ as the oxidant. The experimental results show that the Fe/PMA@CIN-1 composite can act as an efficient heterogeneous catalyst for the epoxidation of cyclooctene. The intramolecular charge transfer between the COFs and the dual sites (PMA and Fe ions), the spatial structure and the nitrogen content of the COFs played critical roles in dispersing and stabilizing the active species, which are closely connected with the activity and stability of the catalysts. A novel efficient heterogeneous catalyst for the epoxidation of olefins via a simple and cost-effective process is provided, and this experiment demonstrates the notable application prospects of the covalent organic skeleton as a catalyst support.