3D-Printed Metal-Organic Frameworks within Biocompatible Polymers as Excellent Adsorbents for Organic Dyes Removal

Three-dimensional (3D) printing technique has received exceptional global attention as it can create a myriad of high-resolution architectures from digital models. In the present study, 3D-printed metal-organic frameworks (MOFs) were shaped into several geometries via direct ink writing, which overcomes the instability and high-pressure drop of powdery MOF during the flow of gas or liquid streams. The inclusion of a blend of calcium alginate and gelatin (CA-GE) as biocompatible binder allowed for easy writing and an enhanced mechanical property. Besides, it was found that the printing geometry (square, hexagon, and circle), MOF loading amount, and MOF size also greatly influenced the adsorptive performance. For instance, the methylene blue adsorption efficiency of CA-GE scaffolds without MOF was only 43.6%, while the printed MOF/CA-GE sample exhibited 99.8% adsorption efficiency at 20 min. Both the inherent microporous structure of MOFs and meso/macroporous structures of the 3D matrix contributed to the excellent adsorption properties towards a variety of organic dyes and their mixtures. Furthermore, the 3D-printed adsorbents can be easily regenerated in dilute acid solution and reused for at least 7 times without performance loss. In contrast, the powdery MOF can only be repeatedly used for at most 2 times.