Fabrication of Hierarchically Mesoporous Multishelled Metal–Organic Frameworks via Template-Induced Assembly/Grinding Strategy for Immobilization of Enzyme and Enhancing Catalytic Performance

Combining biocatalysis and enzyme immobilization in hierarchical porous metal–organic frameworks (MOFs) with multishell structures to enhance catalysis is of great importance but remains underexplored. Herein, a template-droplet-induced assembly/grinding strategy was designed to construct hierarchically mesoporous multishelled MOFs. The approach enabled controllable fabrication of the MOFs via modulating the concentration ratio of soft templates and multiscale defects. An enhanced catalytic platform was established by immobilizing enzymes in the MOFs. Consequently, by altering the growth shell layers and grinding duration, the catalytic performance of the MOFs@enzymes carriers was further promoted due to the generated nanoconfinement effect and suitable conformational space. The proposed mesoporous triple-shelled MOFs@cellulase carrier exhibited improved catalytic performance in converting cellulose into glucose with satisfactory stability and reusability. Additionally, the strategy was extended to prepare other mesoporous MOFs@enzymes carriers with good enzymatic activity and similar architectures. This methodology offers valuable insights into constructing highly efficient MOFs@enzyme-based biocatalysts with hierarchically mesoporous multishell structures by incorporating different enzymes and MOFs.