3D Printing of Covalent Organic Frameworks: AMicrofluidic-Based System to Manufacture Binder-FreeMacroscopic Monoliths
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Sergio Royuela, Semih Sevim, Guillermo Hernanz, David Rodríguez-San-Miguel,Peter Fischer, Carlos Franco, Salvador Pané, Josep Puigmartí-Luis,* and Félix Zamora*
Covalent organic frameworks (COFs) have witnessed outstanding developments in the past 15 years, particularly in optimizing their pore structures, linkages, and variety of monomers used in their synthesis. Yet, a significant challenge remains unaddressed: the processability of COFs into macroscopic architectures with arbitrary shapes, as they are typically obtained as unprocessable powders. This study presents a novel strategy to address this issue by developing a 3D printable ink comprising a colloidal water suspension of COF nanoparticles. A microfluidic device is engineered that provides precise control over the gelation process of the COF-based ink, allowing for a layer-by-layer fabrication. As a result, the direct production of large-scale binder-free COF architectures from digital designs is achieved at room temperature and atmospheric pressure while eliminating the use of toxic organic solvents.
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