Structure‐Controlled Interpenetrated MOF@COF via C−C Linkage for Enhanced Photocatalysis

Abstract Diversifying the connecting junctions will be feasible for the controllable collaboration of metal–organic frameworks (MOFs) and covalent organic frameworks (COFs) to rationally design multifunction‐integrated heterostructures with enhanced performance, yet it is in the nascent stage. Herein, by intelligently exploiting the polymerization of vinyl group, C−C bond is innovatively introduced to construct the core–shell MOF@COF heterostructures with adjustable shell thickness and rare interpenetrated structure. The unique structure endows prepared C−C‐linked MIL‐68@COF−Vs with more superior visible‐light harvesting and photogenerated carrier separation capability, leading to significantly higher photocatalytic activity and faster degradation rate than pristine MIL‐68‐C=Cs, COF−V, and imine‐linked MIL‐68‐NH 2 @COF−V. Further, the customized MIL‐68@COF−V is in situ grown as reusable films with dramatically boosted performance under ambient conditions, which realize the highly efficient degradation of tetracycline within 15 min (96.5 %), rhodamine 6G within 25 min (97.6 %), and phenol within 40 min (95.3 %) by solar drive. This work exhibits the distinctive advantages of C−C junction in the MOF@COF construction, and highlights the application prospect of rational‐designed heterostructure in the treatment of persistent organic pollutants.