Chemically Active, Porous 3D-Printed Thermoplastic Composites

Abstract

Metal-organic frameworks (MOFs) exhibit exceptional properties and are widely investigated because of their structural and functional versatility relevant to catalysis, separations, and sensing applications. However, their commercial or large-scale application is often limited by their powder forms which make integration into devices challenging. Here, we report the production of MOF-thermoplastic polymer composites in well-defined and customizable forms and with complex internal structural features accessed via a standard three-dimensional (3D) printer. MOFs (zeolitic imidazolate framework; ZIF-8) were incorporated homogeneously into both poly(lactic acid) (PLA) and thermoplastic polyurethane (TPU) matrices at high loadings (up to 50% by mass), extruded into filaments, and utilized for on-demand access to 3D structures by fused deposition modeling. Printed, rigid PLA/MOF composites display a large surface area (SA = 531 m g) and hierarchical pore features, whereas flexible TPU/MOF composites achieve a high surface area (SA = 706 m g) by employing a simple method developed to expose obstructed micropores postprinting. Critically, embedded particles in the plastic matrices retain their ability to participate in chemical interactions characteristic of the parent framework. The fabrication strategies were extended to other MOFs and illustrate the potential of 3D printing to create unique porous and high surface area chemically active structures.

CelloMOF: Nanocellulose Enabled 3D Printing of Metal–Organic Frameworks

“…As compared to these techniques, 3D printing offers valuable advantages, such as high reproducibility, fabrication of complex geometries, controlled pore structures, tailored directionality, low cost, time effectiveness, and up‐scalability. However, 3D printing of MOFs usually requires additive materials, such as bentonite clay (as a binder) and polyvinyl alcohol (as a plasticizer) in ethanol, acrylonitrile butadiene styrene, poly(lactic acid), thermoplastic polyurethane matrices, and photopolymers, while demanding high processing temperature of up to 230 °C or ultraviolet curing. 3D printing of a composite containing MOFs has only been investigated to a limited extent.…”

3D‐Structured Monoliths of Nanoporous Polymers by Additive Manufacturing

“…Hence, more common is the printing of composite monoliths. Several recent reports proved the concept to print various MOFs with typical thermoplastic polymers such as acrylonitrile butadiene styrene (ABS) and polylactic acid (PLA) .…”

3D Printing and Digital Processing Techniques in Dentistry: A Review of Literature

“…PLA is a water‐insoluble and bio‐friendly polymer used in biomedical fields . Researchers consider PLA as a rigid polymer matrix . To maximize the grip on PLA filament and help ensure an error‐free printing experience, a baseline measurement has been designed, namely, 3D's custom extruder bolt.…”