Metal–organic frameworks (MOFs) have attracted
considerable
attention as promising platforms for enzyme immobilization due to
their high porosity and ease of preparation. However, the economy
and greenness of the MOF synthesis process and the stability of the
MOF as well as the microporous structure of MOFs limiting the accessibility
of the enzyme and substrate significantly affect their practical applications.
Here, based on a competitive coordination and selective etching strategy,
we propose a general, simple, fast, low-cost, reproducible, and high-yield
synthesis technique for MOF-immobilized enzymes. In the aqueous phase
at room temperature, we achieved rapid encapsulation of β-glucosidase
(β-G) in MOF-74-2-MI by using 2-methylimidazole (2-MI) as a
nucleation accelerator modulator. Followed by selective etching with
tannic acid (TA), a hierarchical porous composite, β-G@TA-MOF-74-2-MI,
was successfully formed. The results showed a significant increase
in mesopore and macropore volumes, leading to a remarkable 6.41-fold
enhancement in catalytic activity compared to the nonetched composite.
Additionally, it exhibited superior temperature resistance and organic
solvent tolerance compared with the free enzyme, along with outstanding
cycling, storage, and crystallization stability. This work represents
a significant advance in the controlled synthesis of hierarchical
porous enzyme@MOF composites, which opens new possibilities for the
efficient biocatalysis of macromolecular substrates.