Creating Multivariate Metal–Organic Frameworks with Hierarchical Structures by Pseudomorphic Transformation as Long-Lasting Catalyst for CO2 Conversion

Engineering hierarchical architectures in multicomponent multivariate metal–organic frameworks (MTV-MOFs) with synergistic catalytic effects is considered a viable pathway to achieve breakthrough catalyst design and address advanced applications that require sophisticated architectures. In this work, we introduced a pseudomorphic transformation strategy into the structural transformation of MOFs, triggering a dual modulation mechanism of the structure and metal valence states via a methanol vapor-mediated dissolution-recrystallization process. The bimetallic metastable MOF structural transformation process enables the simultaneous construction of hierarchical porosity and multivariate metal active sites, breaking through the limitations of traditional single-component modulation in MOFs to achieve triple synergistic engineering, fabricating ultrastable hierarchical multimetal MTV-MOFs with tunable pore size distributions. The resultant hierarchical multivariate HM-CuCo-MOF-74 exhibits long-lasting catalytic activity in the cycloaddition of CO2 with epoxides, maintaining its structural integrity and catalytic performance for at least 40 catalytic cycles. Furthermore, HM-CuCo-MOF-74 demonstrates significantly improved catalytic performance in large molecule substrate applications compared with previously reported heterogeneous catalysts. This work offers novel ideas for designing heterogeneous catalysts with integrated structural controllability, functional tunability, and catalytic sustainability.