Ordered Large‐Pore MesoMOFs Based on Synergistic Effects of TriBlock Polymer and Hofmeister Ion

Abstract Ordered mesoporous metal–organic frameworks (mesoMOFs) were constructed with a uniform pore size up to about 10 nm and thick microporous walls, opening up the possibility for the mass diffusion of large‐size molecules through crystalline MOFs. The synergistic effects based on triblock copolymer templates and the Hofmeister salting‐in anions promote the nucleation of stable MOFs in aqueous phase and the in situ crystallization of MOFs around templates, rendering the generation of a microcrystal with periodically arranged large mesopores. The improved mass transfer benefiting from large‐pore channels, together with robust microporous crystalline structure, endows them as an ideal nanoreactor for the highly efficient digestion of various biogenic proteins. This strategy could set a guideline for the rational design of new ordered large‐pore mesoMOFs with a variety of compositions and functionalities and pave a way for their potential applications with biomacromolecules.