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

Abstract

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 m 2 /g for 1 Me and 1402 m 2 /g for 1 ipr ). For 1 Me , very high CO 2 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 H 2 uptake of 3.2 wt % at 77 K and 1 bar of pressure, which compares well with other benchmark MOFs. For 1 ipr , the H 2 uptake was found to be 2.54 wt % under similar experimental conditions. The significant adsorption of H 2 and CO 2 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 CO 2 and CS 2 into useful chemicals like cyclic carbonates, cyclic trithiocarbonates, and cyclic dithiocarbonates could be achieved.

Highly effective CS2 conversion with aziridines catalyzed by novel [Dy24] nano-cages in MOFs under mild conditions

“…2 Converting CS 2 into high-value products represents an emerging and effective strategy for CS 2 conversion because such a method can yield useful pharmaceuticals and chemical products without any new pollution. 3–6 The cycloaddition of CS 2 with aziridines to thiazolidine-2-thione is one of the effective methods for CS 2 conversion due to its high atom economy and the important applications of thiazolidine-2-thione as an intermediate in organic synthesis and medicinal chemistry. Many homogeneous and heterogeneous catalysts, such as tributylphosphine, 7 amidato lanthanide amide complexes 8 and ion-exchange resin, 9 have been employed and exhibit excellent catalytic activity for this reaction, but these catalytic reactions involve a large amount of the catalysts (10 mol%), or a long reaction time (48 h), which restricts their use in the practical application of CS 2 conversion.…”

Factors Affecting Hydrogen Adsorption in Metal–Organic Frameworks: A Short Review

“…The main benefit of MOFs is their reversible and high-rate hydrogen adsorption process. A reasonable number of H 2 molecules inside the body of MOFs may only be obtained at very low temperatures [ 28 , 29 , 30 , 31 , 32 , 33 , 34 , 35 , 36 , 37 , 38 , 39 , 40 , 41 , 42 , 43 , 44 , 45 , 46 , 47 , 48 , 49 , 50 , 51 , 52 , 53 , 54 ]. To date, MOFs have shown significant progress in applications of gas separation, catalysis, and coordination chemistry.…”

Exploring the Noncovalent Interactions of the Dinuclear Cu(II) Schiff Base Complex with Bovine Serum Albumin and Cell Viability against the SiHa Cancer Cell Line

“…Dinuclear metal complexes containing organic ligands are significantly investigated due to their structural diversity, potential interactions with biomacromolecules, and significant applications in the areas of chemical as well as biological sciences. The structure of polynuclear metal complexes may be tuned by a suitable selection of metal ions and bridging/chelating organic ligands. − In addition, the backbone flexibility, substituent groups, and symmetry of the organic ligands also contribute to form compounds with different structures and physical properties . Schiff base transition-metal complexes are now studied comprehensively regarding these prospective industrial and biological applications.…”