3D Printing of an In Situ Grown MOF Hydrogel with Tunable Mechanical Properties

Due to their precisely modifiable microporosity and chemical functionality, Metal–Organic Frameworks (MOFs) have revolutionized catalysis, separations, gas storage, drug delivery, and sensors. However, because of their rigid and brittle powder morphology, it is challenging to build customizable MOF shapes with tunable mechanical properties. Here, we describe a new three-dimensional (3D) printing approach to create stretchable and tough MOF hydrogel structures with tunable mechanical properties. We formulate a printable ink by combining prepolymers of a versatile double network (DN) hydrogel of acrylamide and alginate, a shear-thinning agent, and MOF ligands. Importantly, by simultaneous cross-linking of alginate and in situ growth of the HKUST-1 using copper ions, we are able to create composites with high MOF dispersity in the DN hydrogel matrix with high pore accessibility. We extensively characterize the inks and uncover parameters to tune modulus, strength, and toughness of the 3D prints. We also demonstrate the excellent performance of the MOF hydrogels for dye absorption. Our approach incorporates all of the advantageous attributes of 3D printing while offering a rational approach to merge stretchable hydrogels and MOFs, and our findings are of broad relevance to wearables, implantable and flexible sensors, chemical separations, and soft robotics.