Metal-Organic Frameworks Housing Active Molecules As Bioinspired Catalysts

Optimization of activity, selectivity, and stability of catalysts for practical application is a long -soughtafter goal. Recent progress in the advancement of rational catalyst design routinely takes queues from nature. Specifically, enzymes are renowned for their high efficiency and selectivity in diverse and significant reactions under mild conditions. Despite the well-known merits of enzymes, they often remain unsuitable for industrial catalysis due to issues, including limited environment (solvent/temperature/ pH) compatibility, considerable structural uncertainty, and highly specific reaction scopes. In the context of bioinspired catalysis design, the development of synthetic heterogeneous catalyst analogs, which may not only mimic enzymes to reproduce or even surpass their performance but also bypass their intrinsic limitations, is thus, desirable and has been extensively studied in the context of porous materials. The metal-organic framework (MOF) is a superior candidate for porous materials towards this goal, thanks to facile and modular preparation, explicit crystalline composition/structure, tunable pore size/environment, and excellent stability. The introduction of active molecular species such as bioactive molecules (e.g., proteins, enzymes, peptides, amino acids, porphyrins) and chemically active molecules (e.g., frustrated Lewis pairs) into metal-organic frameworks (MOFs) via pore encapsulation, chemical postmodification, or bottom -up construction has been shown to facilitate the cooperative enhancement of catalysis through the enforcement of proximity, enhancement of control/activity, and even inducement of unexpected selectivity. In this minireview, we sought to summarize the last 5 years of fruitful progress, exploiting MOFs housing active molecules for substantial catalysis applications, including asymmetric reactions, CO2 conversion (reduction, cycloaddition), biocatalytic H2O2/dye degradation, and so on, and discuss challenges and opportunities in the prospective exploration of these systems towards enzyme mimicry and new -to -nature catalysis.