Metal–organic frameworks (MOFs) are porous hybrid materials with countless potential applications. Most of these rely on their porous structure, tunable composition, and the possibility of incorporating and expanding their functions. Although functionalization of the inner surface of MOF crystals has received considerable attention in recent years, methods to functionalize selectively the outer crystal surface of MOFs are developed to a lesser extent, despite their importance. This article summarizes different types of post‐synthetic modifications and possible applications of modified materials such as: catalysis, adsorption, drug delivery, mixed matrix membranes, and stabilization of porous liquids.

Metal–organic frameworks (MOF) are a new type of porous materials that have great potential for adsorption of voltaic organic compounds (VOCs). These types of materials composed of metal ions and organic ligands are easy to synthesize, have high surface areas, their surface chemistry can be adjusted to the desired application, and they can also have good chemical and thermal stability. Therefore, this work focuses on the synthesis of a highly hydrophobic MOF material called CIM-80, a porous material that is made up of the Al3+ cation and the mesaconate linker. This MOF has a B.E.T. of approximately 800 m2/g and has potential applications for the adsorption of hydrophobic organic compounds. However, its synthesis is expensive and very dirty. Therefore, we have studied the synthesis conditions necessary to achieve high synthesis yields (85%) and materials with high crystallinity and accessible porosity. To achieve these results, we have used urea as a mild deprotonation reagent and modulator as an alternative to NaOH, which is traditionally used for the synthesis of this MOF. Once the synthesis of this material was controlled, its adsorption/desorption behavior of water and organic compounds such as toluene, cyclohexane and m-xylene was studied by means of vapor adsorption isotherms. The results show the hydrophobic character of the material and the greater affinity the material has toward aliphatic compounds than toward aromatic ones, with toluene being the most adsorbed compound, followed by cyclohexane and m-xylene.