Thiophene-Functionalized Cadmium(II)-Based Metal–Organic Frameworks for CO₂ Adsorption with Gate-Opening Effect, Separation, and Catalytic Conversion

Abstract

Two new porous three-dimensional cadmium­(II) metal–organic frameworks (MOFs) containing thiophene-appended carboxylate acid ligands, formulated as [Cd­(L1)­(4,4′-Bipy)] n .2n(DMF) (1) and [Cd­(L2)­(4,4′-Bipy)] n .2n(DMF) (2) [where L1 = 5-{(thiophen-2-ylmethyl)­amino}­isophthalate, L2 = 5-{(thiophen-3-ylmethyl)­amino}­isophthalate, 4,4′-Bipy = 4,4′-bipyridine, and DMF = N,N′-dimethylformamide] have been synthesized and structurally characterized. The gas adsorption analysis of the activated MOFs shows that they specifically capture CO2 (uptake amount 4.36 mmol/g under 1 bar at 195 K) over N2 and CH4. Moreover, both MOFs show a gate-opening–closing phenomenon, which features the S-shaped isotherms with impressive hysteretic desorption during the CO2 adsorption–desorption process at 195 K. Ideal adsorbed solution theory (IAST) calculations of these MOFs displayed that the obtained selectivity values for CO2/CH4 (50:50) and CO2/N2 (15:85) are approximately 8.6–23 and 93–565, respectively. Configurational bias Monte Carlo simulation was performed to understand the mechanism behind the better CO2 adsorption by these MOFs. Catalytic activity of the MOFs for the CO2 fixation reactions with different epoxides to form cyclic carbonates were tested. These MOFs demonstrated a significantly high conversion (94–99%) of epichlorohydrin to the corresponding cyclic carbonate within 8 h of reaction time at 1 bar of CO2 pressure, at 70 °C, and they can be reused up to five cycles without losing considerably their activity.