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The stability of metal–organic frameworks (MOFs) in water affects their ability to function as chemical catalysts, their capacity as adsorbents for separations in water vapor presence, and their usefulness as recyclable water harvesters. Here, we have examined water stability of four node-modified variants of the mesoporous MOF, NU-1000, namely formate-, Acac-, TFacac-, and Facac-NU-1000, comparing these with node-accessible NU-1000. These NU-1000 variants present ligands grafted to NU-1000's hexa-Zr( iv )-oxy nodes by displacing terminal aqua and hydroxo ligands. Facac-NU-1000, containing the most hydrophobic ligands, showed the greatest water stability, being able to undergo at least 20 water adsorption/desorption cycles without loss of water uptake capacity. Computational studies revealed dual salutary functions of installed Facac ligands: (1) enhancement of framework mechanical stability due to electrostatic interactions; and (2) transformation and shielding of the otherwise highly hydrophilic nodes from H-bonding interactions with free water, presumably leading to weaker channel-stressing capillary forces during water evacuation – consistent with trends in free energies of dehydration across the NU-1000 variants. Water harvesting and hydrolysis of chemical warfare agent simulants were examined to gauge the functional consequences of modification and mechanical stabilization of NU-1000 by Facac ligands. The studies revealed a harvesting capacity of ∼1.1 L of water vapor per gram of Facac-NU-1000 per sorption cycle. They also revealed retention of catalytic MOF activity following 20 water uptake and release cycles. This study provides insights into the basis for node-ligand-engendered stabilization of wide-channel MOFs against collapse during water removal. 

Porous metals represent a class of materials where the interplay of ligament length, width, node structure, and local geometry/curvature offers a rich parameter space for the study of critical length scales on mechanical behavior. Colloidal crystal templating of three-dimensionally ordered macroporous (3DOM, i.e., inverse opal) tungsten provides a unique structure to investigate the mechanical behavior at small length scales across the brittle–ductile transition. Micropillar compression tests show failure at 50 MPa contact pressure at 30 °C, implying a ligament yield strength of approximately 6.1 GPa for a structure with 5% relative density. In situ SEM frustum indentation tests with in-plane strain maps perpendicular to loading indicate local compressive strains of approximately 2% at failure at 30 °C. Increased sustained contact pressure is observed at 225 °C, although large (20%) nonlocal strains appear at 125 °C. The elevated-temperature mechanical performance is limited by cracks that initiate on planes of greatest shear under the indenter.