Progress on 3D‐Printed Metal‐Organic Frameworks with Hierarchical Structures

Abstract

Metal‐organic frameworks (MOFs) have attracted considerable attention in numerous applications due to their large surface areas, tunable pore size, and chemical versatility. However, the performance of most MOFs and their related derivatives in applications are still hindered due to their unoptimized form. Hierarchical nano‐micromacropore MOF structure constructed by 3D printing has been shown to guide working species transportation routes, accelerates ion transportation, and increases the accessible area of MOF, thus leading to improved kinetics and enhanced application performances. Nevertheless, there is a lack of a review on 3D‐printed MOFs and their applications that summarizes and promotes this field's progress. This review first introduces the progress of preparing and embedding MOF into structures via 1) MOF coating processes, 2) in situ growth of MOFs, and 3) using presynthesized MOFs to tune the nano‐ and microstructure of MOF. Subsequently, based on various 3D printing technologies, the principles behind various feedstock material preparation and their related printing processes are discussed with respect to the macrostructure. Thereafter, the advances and recent progress of various devices by 3D‐printed MOFs are summarized with detailed analyses and discussion. Finally, an outlook in this promising field is proposed to provide a progression route for 3D‐printed MOFs.

3D printing of cellulose/leaf-like zeolitic imidazolate frameworks (CelloZIF-L) for adsorption of carbon dioxide (CO2) and heavy metal ions

“…37 3D printing offers the processing of the materials into a hierarchical structure with tunable properties. 4 It led to the formation of tunable porous structures between the crystals of MOFs that also offer tunable hierarchical porosity. 3D printed materials advanced MOF applications in several fields, such as water treatment.…”

“…Three-dimensional (3D) printing technologies have become cheaper, and one can find suitable 3D printers for less than €500. [1][2][3][4] They have advanced several applications, including biomedical applications, 5 regenerative medicine, 6,7 tissue engineering, [8][9][10] wound healing, 11 photocatalysis, 12 and water treatment. 13 3D printing can be achieved via several methods including fused deposition modeling (FDM) printing 1 and direct ink writing (DIW or robocasting).…”

“…16,17 Metal-organic frameworks (MOFs) are promising porous materials for several applications. [18][19][20][21][22][23][24] 3D printed MOF monoliths were reported using a variety of supports, 4,[25][26][27][28] including MOF-74, 29 the University of Texas at San Antonio-16 (UTSA-16), 30 Hong Kong University of Science and Technology (HKUST-1), 31 leaf-like zeolitic imidazolate frameworks (ZIF-L), 32 and ZIF-8. [33][34][35][36] This advanced the shaping and processing of MOF materials.…”

3D-Printed MOFs/Polymer Composite as a Separatable Adsorbent for the Removal of Phenylarsenic Acid in the Aqueous Solution

“…44−46 The granulation and hydraulic extrusion molding methods can process MOF powder into various shapes such as balls, flakes, and granules to meet different application needs. 46 However, this molding process causes MOFs to form a dense structure, 47 which is not conducive to the contact of contaminants with the active sites of MOFs. The preparation process of MOF films and MOF gels is relatively complicated.…”

“…3D printing technology is a customizable, fast, and inexpensive way of manufacturing complicated 3D objects, so it offers clear advantages in facilitating MOFs into three-dimensional adsorbents. 46 In recent years, 3D printing of MOF-based materials has received increasing attention worldwide due to the ability to create dimensionally flexible and structurally complicated architectures with high resolution from digital models, and this approach is a good solution to the problems of difficult recycling and secondary contamination of MOFs in the aqueous environment after adsorption. Currently, the commonly used 3D printing methods are direct ink writing (DIW), fused deposition technology (FDM), and light-curing molding technology (SLA).…”