Cycloaddition Reaction Of CO2 Research Articles

Rational Assembly of Three-component Coordination Polymers as Heterogeneous Catalysts for CO2 Cycloaddition and Cyanosilylation Reactions.

Four new coordination polymers based on 5-(((1H-imidazol-2-yl)methyl)amino) isophthalic acid (H3L) and auxiliary ligands (1,10-phenanthroline, 2,2'-bipyridine, and 4,4'-bipyridine), namely, {[Zn(HL)(phen)(H2O)]·2H2O}n (CP 1), {[Ni(HL)(phen)(H2O)]}n (CP 2), {[Ni(HL)(2,2'-bpy)(H2O)]·2H2O}n (CP 3) and {[Cd(HL)(4,4'-bpy)0.5(H2O)]·2H2O}n (CP 4) were rationally assembled. Furthermore, these four CPs were screened as heterogeneous catalysts for CO2 cycloaddition and cyanosilylation reactions under mild conditions. The catalytic experiments showed that CP 1 had the better catalytic performance, excellent substrate tolerance and recyclability for the above two reactions. It is speculated that the excellent activity of CP 1 may be due to the open Lewis base site and the Lewis acidic characteristics of the zinc (II) center. After five cycles, the catalytic activities of CP 1 did not significantly decrease, and the structures remained unchanged. Therefore, the CP 1 was considered efficient and stable heterogeneous catalysts for above the two reactions.

Triazine- and amino-functionalized poly(ionic liquid) heterogeneous catalyst for efficient CO2 conversion under mild conditions

The efficient conversion of atmospheric CO2 into high value-added chemicals remains a persistent challenge. In this study, a novel strategy for the fabrication of triazine- and amino-functionalized poly(ionic liquid)s (PILs) was reported. By virtue of the rich nitrogen species, the newly-developed PILs possessed great potential in CO2 conversion to produce high-value chemicals. The systematic investigation illustrated that rich-nitrogen PILs could promote the cycloaddition reaction of CO2 and epoxides through the intramolecular synergy of multiple active sites. Excellent conversion and selectivity were achieved under the mild conditions without any co-catalysts and solvents. In addition, PIL heterogeneous catalysts could be easily recovered and reused at least several times without obvious loss in activity. The density functional theory calculation demonstrated that the superior catalytic activity of rich nitrogen PILs was attributed to the synergistic effect of hydrogen bond donor and triazine ring in the catalytic process. Our finding thus presents a versatile platform for fabricating multi-functional heterogeneous catalysts for efficient CO2 conversion.

Recent advances in photocatalytic CO2 cycloaddition reaction

Recent advances in photocatalytic CO2 cycloaddition reaction

Construction on ionic organic polymers by multi-components reactions: Experimental and kinetics modeling of efficient CO2-fixation and high iodine vapor adsorption

A series of ionic polymers (DipyBrn, n = 2, 3, 4) have been synthesized under solvothermal conditions using diaminodibenzo-18-crown-6, 4-pyridinecarboxaldehyde and the corresponding bromomethyl monomer in one-pot through multi-components reactions. After comprehensive characterization of these ionic polymers by FT-IR, SEM, TGA, 13C CP MAS NMR, XPS, N2 adsorption isotherm, etc., the performance of CO2 fixation reaction and iodine vapor adsorption were deliberated in details. Notably, the DipyBr3 catalyst exhibited the best conversion yield of 97.6% for CO2 fixation at the controlled conditions, and the preliminary kinetic study indicated that the activation energy (Ea) for CO2 cycloaddition reaction catalyzed by DipyBr3 was determined as 70.66 kJ·mol−1. Furthermore, the study of iodine vapor capture showed that DipyBr4 has a high iodine absorption capacity (5171 mg·g−1).

The efficient and reusable imidazolium-organoboron catalysts for green CO2 insertion reactions in solvent-free under atmospheric and high-pressure conditions

Organoboron compounds that are available in industrial and scientific research were investigated as organocatalysts for the coupling reaction of CO2 into cyclic carbonates as fine chemicals in solvent-free and under sustainable green atmospheric and high-pressure conditions (1 atm and 1.6 MPa, 100 °C, 2 h). This work synthesized a series of imidazolium-organoboron catalysts (IBC1-IBC8) using the eco-friendly and metal-free methodology and characterized by various analysis techniques. These techniques were NMR (1H, 13C, and 11B), UV–Vis, FT-IR, Mass spectrometry, C/H/N analysis, and melting point measurement together with thermal gravimetric analysis (TGA-DTA), respectively. After that, the Lewis acidity of the synthesized imidazolium-organoboron catalysts, which is important for catalytic CO2 conversion studies, was investigated by the traditional Gutmann-Beckett test, and the Lewis acidity order of the target compounds was found at range 54.96–50.36 ppm. In the presence of 0.1 mol% imidazolium-organoboron catalyst (IBC8) and 0.2 mol% DMAP as co-catalyst, 4-chloromethyl-1,3-dioxalan-2-one was obtained as cyclic carbonate from epichlorohydrin in 44.9 % yield and 97.6 % selectivity (1 atm and 100 °C) and in an excellent 97 % yield with 98.9 % selectivity (1.6 MPa and 100 °C) in 2 h without any solvents. After the imidazolium-organoboron catalyst (IBC8) showed efficient catalytic conversion and high selectivity, the effect of different parameters, including the effect of substrate, Lewis acid-base, reaction time, reaction temperature, CO2 pressure, and catalyst amount, was studied for this catalyst. According to the obtained catalytic conversion results, it was also determined that the optimum Cat./ECH ratio for CO2 cycloaddition reactions is 1/1000.

Solvent-free CO2 cycloaddition by one- and two-dimensional sodium coordination polymers based on hydrazonic ligands

We successfully synthesized and characterized four new coordination polymers of sodium: sodium 4-hydroxy-3-{[2-(pyridine-4-carbonyl)hydrazinylidene]methyl}benzene-1-sulfonate (NaL4-Py), sodium 3-[(2-benzoylhydrazinylidene)methyl]-4-hydroxybenzene-1-sulfonate (NaLPh), sodium 3-[(2-acetylhydrazinylidene)methyl]-4-hydroxybenzene-1-sulfonate (NaLMe), and sodium 3-[(2-carbamoylhydrazinylidene)methyl]-4-hydroxybenzene-1-sulfonate (NaLNH2). These polymers were synthesized through a 1:1 condensation reaction of hydrazide derivatives with sodium salicylaldehyde-5-sulfonate monohydrate (NaSalSO3) and were thoroughly characterized using various analytical techniques. The compounds NaLMe and NaLPh, crystallized in the P 1‾ and P21/n space groups, respectively, forming one-dimensional polymers. On the other hand, NaLNH2 and NaL4-Py crystallized in the Cmca and P 1‾ space groups, respectively, forming two-dimensional coordination polymers. The coordination environment of the sodium cation differed among the compounds, with the imine nitrogen atom interfering in NaL4-Py and NaLPh. The sulfonate group exhibited various coordination modes, resulting in the different dimensionalities of the polymers. Compounds NaL4-Py and NaLPh acted as heterogeneous Lewis acid catalysts for the solvent-free cycloaddition reaction of epichlorohydrine and CO2 into valued cyclic carbonate. High selective conversion (68 %) of epichlorohydrin to cyclic carbonate was obtained at mild conditions, 60 °C and 1 bar CO2, after 24 h of reaction.

A MOF@MOF S-scheme Heterojunction with Lewis Acid-Base Sites Synergistically Boosts Cocatalyst-Free CO2Cycloaddition.

The photocatalytic cycloaddition reaction between CO2 and epoxide is one of the most promising green routes for CO2 utilization, for which high performance photocatalysts are intensely desired. Herein, we have constructed an S-scheme heterojunction of MIL-125@ZIF-67 modified by amino groups, which achieves a cyclic carbonate yield of as high as 99% without employing any co-catalyst, outperforming the previously reported photocatalysts. In-situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and in-situ electron paramagnetic resonance (EPR) spectroscopy reveal the important role of photogenerated electron migration from Lewis acid (Co) sites to the O atom of epoxide in triggering its ring-opening (the rate-determining step of CO2 cycloaddition reaction) under the assistance of photogenerated hole. Synergistically and concurrently, the Lewis base (amino groups) sites activate CO2 to CO2*, facilitating the following CO2 cycloaddition. Such a synergistic effect provides a most favorable approach to design efficient heterogeneous photocatalysts with dual/multiple-active sites for CO2 cycloaddition reaction.

Ionic Liquid‐Functionalized Porous Materials for Catalyzing CO2 Cycloaddition Reaction

Ionic liquids (ILs) are incorporated into traditional porous materials to create ILs‐functionalized porous materials, which exhibit excellent absorption capacity and good catalytic activity for CO2. As a result, they are extensively utilized in the chemical conversion of CO2. This paper specifically focuses on the utilization of ILs‐functionalized organic porous materials, ILs‐functionalized inorganic porous materials, and ILs‐functionalized organic‐inorganic hybrid porous materials in the conversion of CO2. The synergistic effects of combining ILs with porous materials in CO2 conversion are thoroughly discussed. Furthermore, an in‐depth analysis is provided regarding the potential prospects and future applications of utilizing ILs‐functionalized porous materials within the broader realm of catalytic CO2 conversion technologies.

An ionic liquid in Core-shell structure: Halogen-free, metal-free bifunctional catalyst for olefin epoxidation and CO2 cycloaddition

We synthesized a core-shell resin structure with abundant architecture and excellent thermal stability through polymerization. Imidazole ionic liquid with varying carbon chain lengths was immobilized on the surface, resulting in the preparation of metal-free, halogen-free core-shell catalysts with different carbon chain lengths via HCO3- exchange. Characterization using FT-IR, XPS, and various techniques revealed the exceptional performance of our synthetic catalyst in terms of its internal structure. After extensive experimentation, we discovered that the synthesized catalyst exhibits dual functionality for epoxidation and CO2 cycloaddition reactions without requiring solvents or co-catalysts. The epoxidation system demonstrated remarkable conversion rates and selectivity while also exhibiting strong recyclability in heterogeneous reactions, according to kinetic parameters, the reaction order of styrene, TBHP and catalyst during epoxidation is approximately 1, the reference factor for this reaction was calculated to be 6.7×109 (L2·mol−2·min−1), with an activation energy of 48.9 kJ/mol obtained from analyzing reaction rates at different temperatures. In the CO2 cycloaddition reaction, our catalyst exhibited an advantage in catalyzing ring-opening reactions, achieving a conversion rate of 95 % for styrene oxide within six hours along with over 99 % selectivity towards cyclic carbonate formation. It is suggested that the epoxide reaction is carried out in steps, and it is inferred that the catalyst PS-ImC4HCO3 and TBHP are produced into peroxy intermediate active species TBA and HCO4, and the reaction between HCO4- and styrene is the determination step of the total reaction. The reaction rate constant k=0.009 of the absolute step is calculated based on the global optimization algorithm

Enhanced catalytic performance for CO2 cycloaddition and Knoevenagel condensation reactions via stable Eu3+ modified Mn-MOF

The construction of MOF-based catalysts containing simultaneous Lewis acid and Lewis base sites has been considered as an efficient approach to enhance chemical fixation of CO2 into value-added products and Knoevenagel condensation reaction. Herein, one novel Eu3+-modified Mn-MOF (Eu3+@Mn-MOF-1) was successfully synthesized by solvothermal synthesis and post-synthesis modification. In Mn-MOF-1, the alternating chains with single and double carboxylate bridges are connected by H2L4− ligands to form a three-dimensional framework with 1D channels along a axis. Interestingly, the activated state of Eu3+@Mn-MOF-1 (noted as Eu3+@Mn-MOF-1a) with the removal of coordinated and lattice H2O molecules displayed excellent thermal stability. Furthermore, it is worth emphasizing that the inner surfaces of Eu3+@Mn-MOF-1a are functionalized by pentiful Lewis acid sites (tri- and penta-coordinated Mn2+ ions and modified Eu3+ ions) and Lewis base sites (uncoordinated Ocarboxylate and Npyridine). By virtue of the abundant co-existing Lewis acid-base sites, Eu3+@Mn-MOF-1a exhibited high catalytic performance for the cycloaddition of CO2 with epoxides and Knoevenagel condensation of aldehydes and malononitrile with preferable repeatability under mild conditions without the requirement of any solvent. Moreover, Eu3+@Mn-MOF-1a performed much higher activity for the cycloaddition of CO2 with epoxides than Mn-MOF-1a under the same conditions. In addition, Eu3+@Mn-MOF-1a also shows the yield of benzylidenemalononitrile can reach 99.9 % at room temperature within 1 h, representing about 1.3-fold increase compared to that of Mn-MOF-1a (76.0 %). The improvement of catalytic performance suggested the contribution of Eu3+ ions to the reaction. Hence, this work provides an efficient approach for the construction of MOFs with Lewis base sites by elaborately designing organic ligands and Lewis acid sites by post-synthetic modification to expose and/or introduce more unsaturated metal sites.

In Situ Pyrolysis of ZIF-67 to Construct Co2N0.67@ZIF-67 for Photocatalytic CO2 Cycloaddition Reaction.

The development of heterogeneous catalysts with abundant active sites is pivotal for enhancing the efficiency of photothermal CO2 conversion. Herein, we report the construction of Co2N0.67@ZIF-67 through the in situ pyrolysis of ZIF-67 under low-temperature pyrolysis conditions. During the pyrolysis process, the crystal structure of ZIF-67 is predominantly preserved concurrently with the formation of Co2N0.67 nanoparticles (NPs) within the ZIF-67 pores. The optimal catalyst Co2N0.67@ZIF-67(450,2) not only possesses high photothermal efficiency but also can efficiently activate CO2. Benefiting from these characteristics, Co2N0.67@ZIF-67(450,2) exhibited significant catalytic activity in the photocatalytic cycloaddition of CO2 and epichlorohydrin. The yield of (chloromethyl)ethylene carbonate reached 95%, which is more than 4 times higher than that of ZIF-67 under visible light irradiation (300 W·m2 Xe lamp, 3 h). This study could offer an alternative approach to enhance the photocatalytic activity of MOFs through low-temperature pyrolysis.

Thorium Cluster Synthesized by a Solvent-Free Flux Approach: The Richest Coordination Diversity and Application Exploration.

The renaissance of research interests in actinide oxo clusters in the past decade arises from both the concerns of radioactive contamination and their potential utility as nanoscale materials. Compared to the uranium cluster, the thorium (Th) cluster shows less coordination variation. Herein, we presented a unique Th cluster (ThC-1) that exhibits the most diverse coordination chemistry found within a single Th cluster via a solvent-free flux synthesis approach. The melt triazole not only offers a unique solvation environment that may be responsible for the coordination diversity in ThC-1 but also represents the first nitrogen-donor capping ligand in Th clusters. The potential utility of ThC-1 as a heterogeneous catalyst was also explored for a classical CO2 cycloaddition reaction. This work offers a novel approach in synthesizing Th clusters, broadening the realm of the structural diversity of Th.

Insight into the Mechanism of CO2 Chemical Fixation into Epoxides by Windmill-Shaped Polyoxovanadate and n-Bu4NX (X = Br, I).

Carbon dioxide (CO2) coupled with epoxide to generate cyclic carbonate stands out in carbon neutrality due to its 100% atom utilization. In this work, the mechanism of CO2 cycloaddition with propylene oxide (PO) cocatalyzed by windmill-shaped polyoxovanadate, [(C2N2H8)4(CH3O)4VIV4VV4O16]·4CH3OH (V8-1), and n-Bu4NX (X = Br, I) was thoroughly investigated using density functional theory (DFT) calculations. The ring-opening, CO2-insertion, and ring-closing steps of the process were extensively studied. Our work emphasizes the synergistic effect between V8-1 and n-Bu4NX (X = Br, I). Through the analysis of an independent gradient model based on Hirshfeld partition (IGMH), it was found that the attack of n-Bu4NX (X = Br, I) on Cβ of PO triggers a distinct attractive interaction between the active fragment and the surrounding framework, serving as the primary driving force for the ring opening of PO. Furthermore, the effect of different cocatalysts was explored, with n-Bu4NI being more favorable than n-Bu4NBr. Moreover, the role of V8-1 in the CO2 cycloaddition reaction was clarified as not only acting as Lewis acid active sites but also serving as "electron sponges". This work is expected to advance the development of novel catalysts for organic carbonate formation.

A confined catalysis strategy: Lewis acid-base (B/Br) and hydrogen bond donor (-OH) multi-functionalized core-shell catalyst for CO2 cycloaddition

In recent years, a significant number of metal-based catalysts were synthesized for the CO2 cycloaddition reaction. However, the leaking of active metal elements resulted in various environmental issues. To prevent the loss of active components and enhance the catalyst lifespan, a confined catalysis strategy involving a multi-functionalized core-shell catalyst with Lewis acid-base (B/Br) and hydrogen bond donor (-OH) was designed. It was noteworthy that B-mSiO2@MCM-IMOH featured multifunctional catalytic active sites, including Lewis acid-base (B/Br) and hydrogen bond donor (-OH), and the cooperative effect of B, Br and -OH significantly improved the catalytic activity. Therefore, B-mSiO2@MCM-IMOH demonstrated outstanding catalytic performance for the CO2 cycloaddition reaction. In addition, the core-shell molecular sieve, serving as a confined catalytic carrier, effectively enhanced the stability and recyclability of the catalyst. Utilizing DFT calculations, a cooperative catalytic mechanism was proposed involving Lewis acid-base (B/Br) and hydrogen bond donor (-OH). The synergistic interaction between B/Br and -OH markedly reduced the energy barrier for the ring-opening of propylene oxide from 58.6 kcal·mol−1 to 21.5 kcal·mol−1, thus facilitating the PO-CO2 cycloaddition reaction.

Synthesis of metal-free benzimidazole-based catalysts and its application in CO2 cycloaddition.

Ionic polymers functionalized with hydroxyl, carboxyl, and amino groups can enhance the catalytic activity of catalysts. However, the straightforward preparation of bifunctional ionic polymers containing abundant ionic active sites and hydrogen bond donors remains challenging. In this study, a series of porous ionic polymers (BZIs) containing different hydrogen bond donors (-NH2, -OH, -COOH) were prepared through a simple one-pot Friedel-Crafts alkylation using benzimidazole derivatives and benzyl bromide. The structures and properties of BZIs were characterized by various techniques such as Fourier-transform infrared spectroscopy, X-ray photoelectron spectroscopy, solid-state nuclear magnetic resonance, and scanning electron microscopy. Among the prepared catalysts (BZI-NH2, BZI-OH, and BZI-COOH), BZI-NH2 exhibited the highest catalytic activity and recyclability, achieving a yield of 97% in the CO2 cycloaddition. The synergistic effect of Br-, hydrogen bond donors (-NH-, -NH2), and N+ in BZI-NH2 was found to contribute to its superior catalytic performance. DFT calculations were employed to study the effect of hydrogen bonds, Br-, and N+ in BZI-NH2 and BZI-OH on the CO2 cycloaddition. Using BZI-NH2 as an example, a mechanism was proposed for the synergistic effect between amino groups and bromide ions in catalyzing the CO2 cycloaddition reaction.

Functionally enhanced polyether-bridged amidopyridinium dicationic ionic liquids for highly efficient and sustainable fixation of CO2 to cyclic carbonates

Task-specific ionic liquids integrated with multi-active sites display promising potential for use in the cycloaddition reaction of CO2 and epoxides. Utilizing the functional enhancement strategy, we successfully synthesized a novel range of polyether-bridged amidopyridinium dicationic ionic liquids (PE-PyDILs) via efficient bisamidation and biquaternization reactions. Under relatively mild reaction conditions, PE-PyDILs can catalyze the coupling of CO2 with various epoxides to produce cyclic carbonates in quantitative yields, demonstrating an enhanced effectiveness and a longer service life compared to previous DILs. At a very low loading of 0.01 mol%, the TON value is as high as 7700. The excellent catalytic performance can be attributed to the intramolecular cooperative activation of epoxides with two amidopyridinium cations bridged by polyether, as supported by the spectroscopic analysis and kinetic studies. This mechanism led to a reduction in activation energy and improved the efficiency of the cycloaddition reaction.

Hydroxyl-functionalized ionic liquid-modified covalent organic frameworks for efficient CO2 cycloaddition conversion

Converting CO2 into high-value chemicals is an essential way to mitigate greenhouse impact and realize sustainable utilization of resources. In this work, the COF materials named X-QCOF (X = OH, OCH3) were synthesized by a three-component Povarov reaction, followed by chemical grafting of hydroxyl‑functionalized ionic liquid into the COFs neutral backbone via quaternization to obtain the hybrid materials IL-X-QCOF (X = OH, OCH3). The resultant IL-X-QCOF can efficiently catalyze the cycloaddition reaction of CO2 and epoxides in the absence of metals, additives and solvents. Among them, IL-OH-QCOF exhibits a yield of 97.2% of cyclochloroallyl carbonate with a high turnover frequency (TOF) value of 217.7. The inherent high specific surface area of the COF-based materials promotes mass transfer efficiency, and meanwhile the abundant hydroxyl groups and bromine anions occurring in the backbone create excellent catalytic effect. Attributed to the chemical grafting approach, the product yield keeps over 90% when IL-OH-QCOF is reused for 6 cycles.

Green and rational design of Ln4Zn2L2 heteromultimetallic complexes for mild and highly efficient CO2 conversion

Reasonable and high efficient utilization of carbon dioxide (CO2) has always been considered as a kind of green and sustainable development strategy. However, the efficient chemical conversion of CO2 into value-added products has been limited due to lack of efficient catalysts. Herein, two novel heterometallic hexanuclear complex catalysts (viz Nd4Zn2L2 (1) and Eu4Zn2L2 (2)) were designed and synthesized, which featuring unique hetero-multinuclear units. The heterometallic hexanuclear complex catalysts not only have multi-bimetallic catalytic sites (Ln3+ and Zn2+) which can absorb more molecules and be beneficial to the improvement of catalytic performance, but also have the potential to further expand the chemical fixation of CO2 with epoxides avoid the harsh reaction conditions. Using the synthesis of propylene carbonate (PC) by cycloaddition reaction of propylene oxide (PO) and CO2 as a model reaction, the as-prepared catalysts and catalytic system showed high turnover frequencies (TOFs) under the mild condition instead of harsh reaction conditions. More importantly, these catalysts can be reused to preserve the structure's integrity and retain their catalytic activity at the same level even after five rounds of catalysis. The excellent regeneration performance indicated that the as-prepared heterometallic hexanuclear complex catalysts can be reused many times. In addition, the catalytic system also exhibited a wide range of substrates for epoxide. These results predict that the proposed heterometallic hexanuclear complex catalysts and catalytic system have great potential toward CO2 adsorption and catalytic conversion. This work may build up a new synthetic route for tailoring more new heterometallic complex catalysts with excellent catalytic activity and applied in various fields of application.

Nitrogen-rich covalent-organic-framework as a recyclable heterogenous catalyst for the efficient cycloaddition of carbon dioxide with epoxides

Carbon dioxide (CO2) can be chemically converted into high-value products, which is not only helps to ease the environmental problems instigated by global warming and has an optimistic effect on economies around the planet. The production of cyclic carbonates is regarded as a promising approach to convert CO2 through the cycloaddition of CO2 with epoxides. However, a major obstacle in this process is the synthesis of environmentally friendly and highly effective heterogeneous catalysts. Here, a novel nitrogen-rich covalent organic framework (CP-COF) was firstly synthesized through a polymerization method of piperazine and cyanuric chloride with 1, 4‐dioxane and used for the aforesaid reaction. A number of analytical methods were employed to verify the chemical composition and the structure of the catalyst. The CP-COF catalyst possessed a significant amount of active nitrogen sites and hydrogen bond donors in it, resulting in a high level of reactivity for the cycloaddition reaction of CO2 with epichlorohydrin in the absence of any solvent and metals, and the yield of chloropropene carbonate (CPC) reached 99 % at 110 ℃, 6 h and 1 MPa CO2 pressure. The CP-COF sample exhibited commendable activity towards a range of epoxides. Moreover, it showed high reusability for the reaction without any loss in the catalytic efficiency.

Porous bi-functional ionic liquid-grafted metal–organic framework for diluted CO2 cycloaddition reaction

Direct utilization of low-concentration CO2 is of importance to mitigate the global warming and reduce energy consumption. Herein, a new bi-functional ionic liquid-grafted material was fabricated for CO2/N2 selectivity and diluted CO2 cycloaddition reaction. Following the preparation of 1-carboxymethyl-3-methoxy ethyl-imidazolium chloride ([CmMOEim]Cl) containing carboxyl and ether group, MIL-53(Al) was used for directly chemical grafting of the ionic liquid to obtain [CmMOEim]Cl@MIL-53(Al). CO2 capture capacity of [CmMOEim]Cl@MIL-53(Al) reached up to 70 cm3 CO2/g sorbent at 25 °C and 0.1 MPa, which was higher than that of two individual components. Cyclopropyl carbonate of 97 % yield was obtained at 110 °C, 3 MPa of initial 50 vol% CO2/N2 pressure and 4 h with 2.4 wt% [CmMOEim]Cl@MIL-53(Al)-0.4 under solventless and co-catalyst-free condition. Various terminal cyclocarbonates were synthesized with above 90 % yield. In addition, the heterogeneous catalyst was separated from reaction system by simple centrifugation and the yield of cyclopropyl carbonate was higher than 90 % after 12 cycles owing to the chemical grafting of [CmMOEim]Cl on MIL-53(Al).