Novel 3D Nitrogen-Rich Metal Organic Framework for Highly Efficient CO₂ Adsorption and Catalytic Conversion to Cyclic Carbonates under Ambient Temperature

Abstract

A novel Lewis acid–base bifunctional Zn­(II)-based MOF-Zn-1 [Zn2L2MA·2DMF] (MA = melamine, H2L = 2,5-thiophenedicarboxylic acid), with abundant micropores and free -NH2 groups was facilely assembled by incorporating zinc­(II) ion with nitrogen-rich melamine and 2,5-thiophenedicarboxylic acid ligands. The constructed MOF-Zn-1 presented an excellent affinity toward CO2 molecules due to the Lewis-base property together with abundant micropores. The Zn active sites could be used for epoxide activation. The acid–base synergistic effects facilitated CO2 conversion into cyclic carbonates under ambient temperature using the porous MOF-Zn-1 as a heterogeneous catalyst. Moreover, the MOF-Zn-1 exhibited satisfied stability and versatility, and it was easy to recycle with no obvious decrease of catalytic activity. Then the feasible synergistic mechanism of MOF-Zn-1/Bu4NBr catalysts for CO2 conversion was proposed.

A Copper Metal–Organic Hydrogel as a Catalyst for SO2 and CO2 Fixation under Ambient Conditions

“…Thus the decrease in the conversion with the increase in bulk of the side chain may be explained by the steric effect of the epoxide side chain. The critical step in the reaction of epoxide with CO 2 is the activation of the epoxide ring by the metal center . With the increase in the bulk of the epoxide, the coordination of the epoxide oxygen to the copper center is more difficult, and thus the conversion to cyclic carbonate decreases with the increase in the size of the epoxide side chain.…”

“…But the selection of the suitable catalyst is crucial for the activation and the successful fixation of carbon dioxide. The transition metal containing MOFs and MOGs, have the potential as heterogeneous catalysts for the fixation of CO 2 . MOGs have more advantages over the MOFs, as syntheses of MOGs are much more straightforward.…”

Bi-functional heterogeneous catalysts for carbon dioxide conversion: enhanced performances at low temperature

“…However, this goal is usually achieved employing imidazolium or more oen ammonium salts in homogeneous phase. [40][41][42][43][44][45] It should be mentioned that a direct comparison with the literature is hampered by the huge differences in the reaction conditions employed for the synthesis of cyclic carbonates including presence of solvent, substrate to catalyst molar ratio, nature of nucleophile, use of co-catalyst, temperature, pressure and reaction time. These difficulties can be partially reduced if the catalysts are compared in terms of turnover number or turnover frequency (TOF dened as TON/ time).…”

Metal and Co‐Catalyst Free CO2 Conversion with a Bifunctional Covalent Organic Framework (COF)

“…[10][11][12][13][14][15][16] However, they always need a large amount of cocatalyst as well as high reaction temperature and CO 2 pressure, which complicate the separated and synthetic processes with extra cost and environment pollution. [17,18] Thus, it is in urgent need to rationally construct high-efficient and genuine heterogeneous catalytic systems for CO 2 conversion.…”