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-NH2@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.