Combining In Situ Techniques (XRD, IR, and 13C NMR) and Gas Adsorption Measurements Reveals CO2-Induced Structural Transitions and High CO2/CH4 Selectivity for a Flexible Metal–Organic Framework JUK-8

Flexible metal-organic frameworks (MOFs) are promising materials in gas-related technologies. Adjusting the material to processes requires understanding of the flexibility mechanism and its influence on the adsorption properties. Herein, we present the mechanistic understanding of CO 2 -induced pore-opening transitions of the water-stable MOF JUK-8 ([Zn(oba)(pip)] n , oba 2- = 4,4'-oxybis(benzenedicarboxylate), pip = 4-pyridyl-functionalized benzene-1,3-dicarbohydrazide) as well as its potential applicability in gas purification. Detailed insights into the global structural transformation and subtle local MOF-adsorbate interactions are obtained by three in situ techniques (XRD, IR, and 13 CO 2 -NMR). These results are further supported by single-crystal X-ray diffraction (SC-XRD) analysis of the solvated and guest-free phases. High selectivity toward carbon dioxide derived from the single-gas adsorption experiments of CO 2 (195 and 298 K), Ar (84 K), O 2 (90 K) , N 2 (77 K), and CH 4 (298 K) is confirmed by high-pressure coadsorption experiments of the CO 2 /CH 4 (75:25 v/v) mixture at different temperatures (288, 293, and 298 K) and in situ NMR studies of the coadsorption of 13 CO 2 / 13 CH 4 (50:50 v/v; 195 K).