Formulation of Metal–Organic Framework Inks for the 3D Printing of Robust Microporous Solids toward High-Pressure Gas Storage and Separation

Abstract

3 Shaping of metal-organic frameworks (MOFs) has become increasingly studied over the past few 4 years because it represents a major bottleneck toward their further applications at larger scale. 5 MOF-based macroscale solids should present similar performances to their powder counterparts along with adequate mechanical resistance. 3D printing is one of the promising technologies as it 7 allows the fast prototyping of materials at the macroscale; however, the large amounts of added 8 binders have a detrimental effect on the porous properties of the solids. Herein, a 3D printer was 9 modified to prepare a variety of MOF-based solids with controlled morphology from shear-10 thinning inks containing 2-hydroxyethyl cellulose. Four benchmark MOFs were tested for this 11 purpose: HKUST-1, CPL-1, ZIF-8 and UiO-66-NH 2. All solids are mechanically stable up to 0.6 12 MPa of uniaxial compression and highly porous with BET specific surface areas lowered by 0 to 13-25%. Furthermore, these solids were applied to high pressure hydrocarbon sorption (CH 4 , C 2 H 4 14 and C 2 H 6) and presented consequent methane gravimetric uptake (UiO-66-NH 2 , ZIF-8, and 15 HKUST-1) and highly preferential adsorption of ethylene of ethane (CPL-1).

Chiral Macroporous MOF Surfaces for Electroassisted Enantioselective Adsorption and Separation

“…[11][12][13][14][15][16]31 Metal-organic frameworks (MOFs) are very useful crystalline hybrid porous materials, based on the coordination chemistry between metal nodes and organic ligands. [32][33][34][35][36][37][38][39][40][41][42][43][44][45][46][47][48] MOFs have attracted considerable attention in the context of various potential applications [32][33] such as gas storage, [34][35] drug delivery, 39 sensing, 40 catalysis, 38,[41][42] molecular recognition, 43 electronics 44 , separation, 45 and water-gas shift reactions, 49 due to their unique properties, such as high surface area, crystalline structure and tunable pore size. In addition, it is possible to generate chiral MOF surfaces by introducing chiral ligands.…”

Beyond Frameworks: Structuring Reticular Materials across Nano‐, Meso‐, and Bulk Regimes

“…This approach largely allows the retention of the porosity and enables high loading and low amounts of binder in the final monoliths. Often a type of gel composite is used here, such as one based on hydroxyethylcellulose [81a, 152g, 162] . Embedding the reticular material in a polymer matrix allows printing by the typical melt extrusion used in commercial 3D printers, but this approach does not allow high loading and a reduction in the porosity can be observed [163] .…”

Two‐dimensional metal organic frameworks for biomedical applications

“…These hybrid composites successfully maintained mechanical rigidity, high porosity, and increased surface area. Another study combined a variety of MOF powders with hydroxyethyl cellulose as a binder and poly(vinyl alcohol) as a a plasticizer to achieve optimal shear‐thinning properties that is otherwise difficult to achieve in inks containing powders (Dhainaut, Bonneau, Ueoka, Kanamori, & Furukawa, 2020). These inks were then 3D printed via extrusion to form solids with similar structural and porous properties as that of the powders.…”