In this review, we have portrayed the structure, synthesis and applications of a variety of biomimetic MOFs from an unprecedented angle. Synthetic MOF analogues of five distinct enzymes: phosphotriesterase, hydrogenase, cytochrome P450, chymotrypsin and carbonic anhydrase, have been discussed with their skeletal comparison to actual enzymatic active sites as reference, and an explanation of catalytic pathways from the mechanistic cycle of the corresponding enzymes is depicted. We demonstrated critically each of the five discrete situations by assimilating available benchmark researches in an attempt to provide a concise literature source on the ingenious design strategies and versatile biomimetic applications of this domain of materials.

Four highly porous covalent organic frameworks (COFs) containing pyrene units were prepared and explored for photocatalytic H2O2 production. The experimental studies are complemented by density functional theory calculations, proving that the pyrene unit is more active for H2O2 production than the bipyridine and (diarylamino)benzene units reported previously. H2O2 decomposition experiments verified that the distribution of pyrene units over a large surface area of COFs plays an important role in catalytic performance. The Py‐Py‐COF though contains more pyrene units than other COFs which induces a high H2O2 decomposition due to a dense concentration of pyrene in close proximity over a limited surface area. Therefore, a two‐phase reaction system (water‐benzyl alcohol) was employed to inhibit H2O2 decomposition. This is the first report on applying pyrene‐based COFs in a two‐phase system for photocatalytic H2O2 generation.

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