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

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 6 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-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 0.612 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).