Metal–Organic Frameworks of Cu(II) Constructed from Functionalized Ligands for High Capacity H2 and CO2 Gas Adsorption and Catalytic Studies

Two Cu(II)-based metal-organic frameworks (MOFs) having paddle-wheel secondary building units (SBUs), namely, 1_Me and 1_ipr, were synthesized solvothermally using two new bent di-isophthalate ligands incorporating different substituents. The MOFs showed high porosity (BET surface area, 2191 m²/g for 1_Me and 1402 m²/g for 1_ipr). For 1_Me, very high CO₂ adsorption (98.5 wt % at 195 K, 42.9 wt % at 273 K, 23.3 wt % at 298 K) at 1 bar was found, while for 1_ipr, it was significantly less (14.3 wt % at 298 K and 1 bar, 54.4 wt % at 298 K at 50 bar). 1_Me exhibited H₂ uptake of 3.2 wt % at 77 K and 1 bar of pressure, which compares well with other benchmark MOFs. For 1_ipr, the H₂ uptake was found to be 2.54 wt % under similar experimental conditions. The significant adsorption of H₂ and CO₂ for 1_Me could be due to the presence of micropores as well as unsaturated metal sites in these MOFs besides the presence of substituents that interact with the gas molecules. The experimental adsorption behavior of the MOFs could be justified by theoretical calculations. Additionally, catalytic conversions of CO₂ and CS₂ into useful chemicals like cyclic carbonates, cyclic trithiocarbonates, and cyclic dithiocarbonates could be achieved.