Hydrophobic Metal–Organic Frameworks: Assessment, Construction, and Diverse Applications

Tens of thousands of metal–organic frameworks (MOFs) have been developed in the past two decades, and only ≈100 of them have been demonstrated as porous and hydrophobic. These hydrophobic MOFs feature not only a rich structural variety, highly crystalline frameworks, and uniform micropores, but also a low affinity toward water and superior hydrolytic stability, which make them promising adsorbents for diverse applications, including humid CO(2) capture, alcohol/water separation, pollutant removal from air or water, substrate‐selective catalysis, energy storage, anticorrosion, and self‐cleaning. Herein, the recent research advancements in hydrophobic MOFs are presented. The existing techniques for qualitatively or quantitatively assessing the hydrophobicity of MOFs are first introduced. The reported experimental methods for the preparation of hydrophobic MOFs are then categorized. The concept that hydrophobic MOFs normally synthesized from predesigned organic ligands can also be prepared by the postsynthetic modification of the internal pore surface and/or external crystal surface of hydrophilic or less hydrophobic MOFs is highlighted. Finally, an overview of the recent studies on hydrophobic MOFs for various applications is provided and suggests the high versatility of this unique class of materials for practical use as either adsorbents or nanomaterials.