Agile Construction of Porous Organic Frameworks Pending Carboxylic Acids and Imidazolium-Based Ionic Liquids for the Efficient Fixation of CO₂ to Cyclic Carbonates

Abstract

The design and facile preparation of ionic liquids (ILs)-functionalized polymer materials is a hot research topic due to their potential wide applications. Herein, taking the reaction advantage of a cyclic anhydride with an alcoholic compound to atom-economically generate a carboxyl ester pending a carboxylic acid moiety, porous organic framework (POF) materials pending carboxylic acids and imidazolium-based ILs (CILs-POF m ) were facile synthesized via the acylation reaction of hydroxyl group-functionalized ILs with a styrene maleic anhydride copolymer. The CILs-POF m material properties were facilely adjusted by changing the molar ratio of the mono-hydroxyl-functionalized ILs to the dihydroxyl-functionalized ILs. CILs-POF m materials showed abundant mesoporous structures with a porous diameter of approximately 23.83–48.16 nm, a surface area of up to 274.4 m2 g–1, and a superior CO2 adsorption capacity of 1.71–2.14 mmol g–1 at 273 K and 1 atm. As a proof of concept application, the coupling reaction of epoxides with CO2 to produce cyclic carbonates was studied by using the CILs-POF m materials as catalysts under solvent-free and co-catalyst-free conditions. The findings indicated that the CILs-POF0.5 exhibited a satisfactory catalytic activity and reusability for a large scope of epoxides. Based on the experimental results and density functional theory (DFT) simulations, a synergetic catalytic mechanism was proposed based on the pended carboxylic acidic groups and IL groups. This study not only provided an atom-economic strategy to prepare POFs pending both carboxylic acids and ILs, but also showed new insights into the design of functionalized POF materials with great application potential in energy storage materials, separation, and green catalysis.

Thermally activated bipyridyl-based Mn-MOFs with Lewis acid–base bifunctional sites for highly efficient catalytic cycloaddition of CO2 with epoxides and Knoevenagel condensation reactions

“…[8][9][10] In fact, CO 2 molecules as the C1 feedstock have been intensively developed and converted into value-added chemicals such as dimethyl carbonates, formic acid and cyclic carbonates. [11][12][13][14][15][16][17][18] Among them, the cycloaddition of CO 2 and epoxides to afford cyclic carbonates is more significant because of its 100% atom economy and the potential of cyclic carbonates to be used in industries. Great efforts have been devoted to preparing versatile catalysts such as ionic liquids, zeolites, porous organic polymers and metal-organic frameworks (MOFs) for CO 2 capture and further conversion into cyclic carbonates.…”

Carbon Dioxide Cycloaddition to Epoxides Promoted by Nicotinamidium Halide Catalysts: A DFT Investigation

“…Therefore, efficient catalysts should possess good nucleophilic character in order to be able to activate the epoxide ring and facilitate its opening, and good capability as leaving group to speed up the ring closure step. Several catalytic systems have shown high activity and stability for this reaction, including ionic liquids, [28–30] bifunctional or binary complexes, [31–33] and quaternary onium salts [26,34] …”

Newly synthesized imidazolium precursors for CO2utilization and sequestration: aproticversusprotic salts

“…In this respect, the synthesis of cyclic carbonates (CCs) from CO 2 and epoxides is a prominent example of CO 2 utilization that could be driven using a wide range of inorganic/ (organo)catalysts. 1,2 The latter directed our attention towards using cheap, commercially available, abundant building blocks that exist in biomaterials, [3][4][5] which can be easily turned into covalent 6 /metal 7 organic frameworks, hybrid materials, 8 ionic liquids (ILs), 9 and porous organic polymers. 10 Imidazole/(ium) based heterocyclic compounds have attracted considerable interest in the last few decades due to their versatile properties as natural, 11 agricultural, and biologically active products and active pharmaceutical ingredients.…”

“…In this respect, the synthesis of cyclic carbonates (CCs) from CO 2 and epoxides is a prominent example of CO 2 utilization that could be driven using a wide range of inorganic/(organo)catalysts. 1,2 The latter directed our attention towards using cheap, commercially available, abundant building blocks that exist in biomaterials, 3–5 which can be easily turned into covalent 6 /metal 7 organic frameworks, hybrid materials, 8 ionic liquids (ILs), 9 and porous organic polymers. 10…”