Construction and shaping of polyoxometalate‐based covalent organic framework for boosting one‐pot CO2 conversion

Abstract Covalent organic frameworks (COFs), as potential heterogeneous catalysts, face the problem of single functional active sites in one‐pot catalysis. Herein, a polyoxometalate (POM) species, phosphomolybdic acid hydrate (PMA, H 3 PMo 12 O 40 ) was stably integrated into the nanocages of an ionic COF (EB‐TFP). Considering practical applications, the resulting composite (EB‐TFP/PMA) powder was shaped into monolithic pellets with sufficient crushing strength and thermal stability. These materials were used in a one‐pot reaction of CO 2 and olefins to obtain value‐added cyclic carbonates. Detailed activity evaluations revealed that the excellent catalytic performance (90% of main yield under the conditions of 80 C, 1 bar, 24 h and no co‐catalysts) of EB‐TFP/PMA arose from the synergistic effect of acid/base sites. The pellets also showed satisfactory catalytic performance (83% of yield under the same conditions) and good reusability. This study highlights the potential of COFs as platforms to construct synergistic active sites tailored for one‐pot catalysis.