Fabrication of metal-organic frameworks macro-structures for adsorption applications in water treatment: A review

Metal-organic frameworks (MOFs) are emerging porous organic-inorganic hybrid materials composed of metal centers/clusters and various organic ligands, which are widely used in water and wastewater treatment applications due to their large specific surface area, high porosity, tunable chemical properties and abundant active sites. However, pure MOFs powders have limitations such as poor recovery, blocked pipelines and secondary contamination in practical water treatment processes. Enabling the magnetization of MOFs or immobilizing MOFs as macroscopic MOFs materials offers new opportunities to improve solid-liquid separation performances of powdered MOFs. Besides, macroscopic MOFs materials with outstanding adsorption performance and mechanical properties by the combining of 3D particles and 2D nanosheets MOFs with other substrates are widely used for water treatment. This paper provides a comprehensive review of recent advancements in MOFs macrostructures. We firstly summarized the synthesis strategies of magnetic MOFs composites and various MOFs macro-structures such as hydrogels/aerogels, membranes, beads/spheres, others composites, etc. which can be constructed by various methods, including in-situ growth, solvothermal method, direct mixing, self-assembly, layer-by-layer growth, etc. Innovative preparation strategies to improve the mechanical properties of MOFs macro-structures were highlighted. Next the article discusses its application for adsorptive removal of various pollutants (i.e., dyes, heavy metal ions, oils and organic pollutants) from water. Finally, the challenges of macroscopic MOFs materials and their practical applications are presented, while future research directions to overcome these existing limitations are also pointed out.