AbstractThe presence of shape‐ and size‐selective catalysts in various catalytic reactions is of paramount importance. Metal‐organic frameworks (MOFs) possess a distinctive characteristic of lacking in‐accessible dead spaces, owing to their well‐structured nature. The effective separation of active sites within MOFs is facilitated by their exceptionally high surface area, which allows for a high density of active sites per unit volume of the catalyst. In this comprehensive review article, we delve into one of the most critical and practical features of MOFs: their ability to modify and engineer the structure of these materials. This structural engineering approach enables the attainment of desired physical, chemical, and surface properties, particularly in the realm of heterogeneous catalysts. The article encompasses several key areas, including surface functionalization within MOFs, synthesis of novel enzyme‐inspired MOFs, creation of mesoporous MOFs, development of porous structures utilizing MOFs, and engineering of structural limitations in MOFs. These rapidly advancing and highly applicable topics, especially in the field of heterogeneous catalysts, are thoroughly investigated and analyzed within the purview of this comprehensive review article.
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