Chemical Fixation Of Carbon Dioxide Research Articles

The Flower-Shaped Co (II) and Cu (II) Phthalocyanine Polymers as Highly Efficient and Stable Catalysts for Chemical Fixation of CO2 to Cyclic Carbonate

New flower-shaped metallophthalocyanine polymers (THB-4-M, M = Co, Cu) have been synthesized by using 1,3,5-Tri(4-hydroxyphenhyl) benzene (THB) as rigid and contorted units to control the morphology under the solvothermal method. The polymers were characterized using FT-IR, UV-vis, SEM, TGA, and XPS. These polymers were applied as heterogeneous catalysts for the chemical fixation of carbon dioxide (CO2) to cyclic carbonates without solvent. The influence of reaction parameters and different metal centers on the catalytic performance were studied in detail. Under optimal conditions, the catalysts showed high conversion (49.9–99.0%), selectivity (over 85%), and reusability at ambient conditions (at 1 bar CO2).

Amine Functionalization of Channels of Metal-Organic Frameworks for Effective Chemical Fixation of Carbon Dioxide: A Comparative Study with Three Newly Designed Porous Networks.

Catalytic transformation of CO2 into value-added chemical products can provide an appropriate solution for the raising environmental issues. To date, various metal-organic frameworks (MOFs) with transition metal ions have been explored for CO2 capture and conversion, but alkaline earth metal-based MOFs are comparatively less studied. Metal ions like Sr(II) having relatively large radius give rise to a high coordination number resulting in higher stability of the MOFs. Moreover, the introduction of N-rich functional group in organic linker like -NH2, -CONH- and triazole into MOF backbone enhance their CO2 capture and conversion efficiency. Herein, the effect of amine group on the catalytic efficiency of MOFs for CO2 cycloaddition with epoxides under solvent free and ambient conditions are presented. The di-carboxylates, such as 5-aminoisophthalate (AmIP) and 5-bromoisophthalate (BrIP) were utilized to synthesize Sr(II) based MOFs. The Zn(II) MOF was synthesized using tetra-carboxylate containing amide spacer (OAT) and 4-amino-4H-1,2,4-triazole (AMT). All three MOFs exhibited porous networks with guest available volume ranging from 15 to 58 %. The catalytic efficiency of the MOFs towards carbon dioxide fixation reaction was explored. The catalytic performances revealed that the presence of amine group in the channels enhances the catalytic efficiency of the MOFs.

Synthesis and characterization of catalytic active oxazolidine/Schiff complexes using 2-quinoline formaldehyde and tris-base for carbon dioxide chemical fixation

Catalytic chemical fixation of carbon dioxide to high value-added chemicals has attracted extensive attention and the discovery of new catalytic system has always been a research hotspot in carbon dioxide chemistry. Three complexes were synthesized by using 2-quinoline formaldehyde and tris-base precursor through Schiff base reaction and characterized. Compound Co[L1]2Cl2·2H2O (1) and compound Ni[L1]2Cl2·2H2O (2) are two mononuclear complex with derived schiff base ligand (L1 = 2-(hydroxymethyl)-2-((quinolin-2-ylmethylene)amino)propane-1,3-diol), while compound Cu2[L2]2Cl2∙2CH3OH (3) is a dinuclear complex containing derived deprontonated ligand (L2 = (2-(quinolin-2-yl)oxazolidine-4,4-diyl)dimethanol) The self-assembly process of these complexes were monitored by ESI-MS. The catalytic explore for the cycloaddition of CO2 and different reaction substrates and preliminary kinetic studies shows that all complexes are active and the reaction is an intramolecular Lewis acid-base catalytic mechanism. This is the first report of oxazolidine complex/ tetrabutylammonium halide catalyst in for cycloaddition of epoxides and CO2 reaction and the complex 3 is more active than the other two complexes, which provides new notions for the design and solicitation of Schiff base/oxazolidine catalysts.

Synthesis of the oleylamine coated mesoporous Fe3O4 nanospheres and their application towards the efficient chemical fixation of carbon dioxide

The present work reports the successful coating of Fe3O4 nanospheres with oleylamine utilizing a single-step solvothermal technique and its application to carbon dioxide's capture and chemical fixation. The existence of the pure cubic spinel phase of Fe3O4 was established by X-ray diffraction. Fourier transform infrared spectroscopy revealed vibrations corresponding to the oleylamine structure, affirming the coating of oleylamine on Fe3O4 nanospheres. X-ray photoelectron spectroscopy further confirmed the presence of oleylamine on the Fe3O4 surface, along with the constituent elements Fe and O. The nanospheres exhibited a spherical shape with an average diameter of ∼17 nm, shown by morphological investigations. Magnetic properties exhibited a Verwey transition at ∼114 K and a saturation magnetization of ∼60 emu/g. The surface area measurements revealed a pore volume of 0.0717 ccg−1 and surface area of 30.558 m2g-1. The existence of oleylamine on the surface of Fe3O4 nanospheres facilitated the capture of CO2 through chemisorption due to the amine group's high selectivity and the nanospheres' large surface area. In the presence of styrene oxide and tetra-n-hexyl ammonium bromide (THAB), the oleylamine-coated Fe3O4 nanospheres successfully converted CO2 to styrene carbonate. The magnetic core and high thermal stability of the material make it suitable for recyclability for the fixation of CO2 into products with added value. This work presents a promising approach for CO2 capture and utilization using Fe3O4 nanospheres coated with oleylamine, with potential applications in carbon capture and utilization technologies.

Designed synergetic bifunctional catalyst based on diverse nucleophilic-functionalized sites for high-efficient CO2 cycloaddition under co-catalyst and solvent-free conditions

Nucleophilic substitutes provide a new platform to design and synthesize novel bifunctional heterogeneous catalysts for carbon dioxide cycloaddition reaction with epoxides. Herein, in this work, UMCM-15 was fabricated and modified with various nucleophilic ligands containing bromine, amine and hydroxyl functional groups. The resultant prepared compounds were utilized as bifunctional synergetic catalysts for the chemical fixation of carbon dioxide. The catalysts can efficiently catalyze epoxides and carbon dioxide under relatively mild conditions in the absence of co-catalyst and solvent. The contemporaneous presence of Lewis acid and basic centers in the framework resulted in high catalytic activity and turnover number (TON) value for the production of cyclic carbonates compared to other reported compounds indicating superiority of the synthesized catalysts. Among diverse applied bifunctional catalysts, bromine-functionalized frameworks exhibited the highest catalytic performance owing to the presence of multiple electron pairs and the great tendency to donate electron pairs.

Metal–organic frameworks with Lewis acid-base sites as highly efficient catalyst for the cycloaddition of carbon dioxide

The chemical fixation of carbon dioxide (CO2) into high value-added chemicals like cyclic carbonates is an effective strategy to solve the energy and ecological issues. Metal-organic frameworks (MOFs) can efficiently catalyze the reaction due to their diverse structures and accessible active sites, herein, two novel MOFs have been successfully constructed based on bi-functional ligand 4-(2, 4-dicarboxylphenyl)-4, 2’: 6′, 4″-terpyridine) (H2dcptpy). The Fourier-transform infrared (FT-IR) spectra data indicated complete de-protonation of the H2dcptpy ligand, their structures have been refined and formulated as [Co(dcptpy)]∙DMF∙6H2O (MOF 1) with a large BET surface areas of 3.4 m2/g and [Cu(dcptpy)(H2O)2] (MOF 2). They both exhibit a three-dimensional network structure with microporosity and contain Lewis acid-base sites located on the surface of the pores. The good purity and stability of the as-synthesized samples were adequately characterized by powder X-ray diffraction (PXRD) and thermogravimetric analysis (TGA). Remarkably, a series of cycloaddition reactions of epoxides with CO2 show that MOF 1 has excellent heterogeneous catalytic activity for cyclic carbonate of epibromohydrin and butyl glycidyl ether, and almost complete conversion can be achieved even under mild conditions (1 bar CO2, 80 °C, 12 h and solvent-free). Therefore, MOF 1 has the potential to be a catalyst material for CO2 conversion.

Chemical fixation of carbon dioxide into cyclic carbonates by multi-hydroxyl carboxylic acid ionic liquids under atmospheric pressure

Transformation CO2 to valuable chemical products is a favorable way for reducing CO2 emissions. However, the developed methodologies usually suffer from harsh reaction conditions. In this work, a series of ionic liquids featuring anions with multiple hydroxyl carboxylic acid moieties (MHCAIL1–5) were facilely synthesized, which exhibiting remarkable catalytic activity in conversion CO2 and various epoxides to cyclic carbonates without metal, co-catalysts, solvents and halogen under atmospheric pressure. The hydroxyl groups and carboxylate anion in ILs serve as hydrogen bond donors and nucleophiles to activate epoxides, ensuring exceptional conversion. Notably, the catalytic performance of MHCAIL-5 resulted in 99 % conversion of epichlorohydrin and 99 % selectivity of chloropropene carbonate at 80 ℃ within 3 h at atmospheric pressure. Proposed mechanism has been postulated according to NMR, FT-IR and Mass spectrometry results. Furthermore, due to the high thermodynamic and chemical stability of ionic liquids, this catalytic system demonstrated excellent recyclability.

Facile synthesis of InIII-salen complexes from indium metal and their use as catalysts for the chemical fixation of carbon dioxide in mild conditions

An alternative, very simple and improved route to obtain indium(III) tetrahaloindate salts of tetrabutylammonium (TBA)[InX4] – 1a (X = Cl), 1b (X = Br) and 1c (X = I) – in high yields (74 – 82%) was developed. Indium(III) tetrahaloindates were then used as starting materials for the synthesis of In(salen)X complexes 2a (X = Cl, 88%), 2b (X = Br, 94%) and 2c (X = I, 88%). Compounds 2a-c were characterized by FT-IR, Raman, and 1H and 13C NMR spectroscopies. The In-salen complexes were able to promote the CO2 cycloaddition reaction with styrene oxide in mild and solvent-free conditions; complex 2a presented the best performance in the initial screening, achieving quantitative conversion (>99%). The parameters of the catalytic system were optimized, and a series of epoxides were tested as substrates for the production of cyclic carbonates with conversions varying from 38% to quantitative. The present study provides a simple method to cheaply and easily prepare indium(III) complexes and employ them to produce value-added chemicals from CO2.

Chemical Fixation of Carbon Dioxide into Cyclic Carbonates Catalyzed by Porous Materials

AbstractThe reaction of carbon dioxide (CO2) with epoxide to generate cyclic carbonates is one of the most effective chemical fixation methods. The catalytic system significantly affects the carbon fixation efficiency of the reaction. Among the reported catalytic systems, porous materials as heterogeneous catalysts have attracted significant attention. This study aimed to summarize porous materials that catalyzed the conversion of CO2 into cyclic carbonates, including metal organic frameworks, covalent organic frameworks, poly(ionic) liquids, hyper crosslinked polymers, conjugated porous polymers and others. The study analyzed the catalytic properties of these materials and outlined future research directions.

Visible-light promoted chemical fixation of carbon dioxide with epoxide into cyclic carbonates over S-scheme CdS–CeO2 photocatalyst

Generally, cyclic carbonates were produced from the cycloaddition of carbon dioxide (CO2) with epoxides over supported nanoparticles at high temperature and pressure conditions. Reducing the reaction temperature and using renewable energy sources would be highly beneficial in the sustainable production of cyclic carbonates from waste CO2. This work introduces efficient and effective production of cyclic carbonates from CO2 and epoxides over supported CeO2 nanoparticles under visible light conditions. The highest yield and selectivity were 96% and 99%, respectively, achieved in the polar protic solvent that diminished the energy barrier of the reaction. The basic surface sites at CeO2 adsorbed a high amount of CO2, favouring the corresponding cyclic carbonates’ high yields within a short span. Additionally, spectroscopic and microscopic techniques characterized the nanocomposites fabricated.

Catalytic Systems for the Effective Fixation of CO2 into Epoxidized Vegetable Oils and Derivates to Obtain Biobased Cyclic Carbonates as Precursors for Greener Polymers

The chemical fixation of carbon dioxide by cycloaddition to biobased epoxides, e.g., vegetable oils, fatty acids, etc., is an efficient, sustainable, and clean strategy to obtain biobased cyclic carbonates. These can be used as feedstocks for the synthesis of environmentally friendly biobased polymers as an alternative to polymers used in daily life such as polyurethanes (PUs) and/or polycarbonates (PCs). Nevertheless, this reaction is not trivial at all due to both the low reactivity of the CO2 molecule and the nature of the needed substrates (biobased epoxides) where the epoxide groups are internal and sterically hindered, hampering the CO2 cycloaddition reaction. Therefore, the design of efficient catalytic systems to overcome these hurdles is mandatory. Most of the catalytic systems developed for this transformation aim to facilitate the rate-determining step in the CO2 cycloaddition catalytic cycle. They comprise an ionic liquid or an ionic compound with a nucleophilic anion alone or in the presence of a cocatalyst to assist the epoxide ring-opening. The most commonly used catalyst is tetrabutylammonium bromide [TBA][Br] ionic liquid, but other ammonium-, phosphonium-, and sulfonium-based ionic liquids in combination or not with a cocatalyst have also been disclosed in the literature. This Review presents a structured overview of the reported catalytic systems, both homogeneous and heterogeneous catalysts, employed in the transformation of any epoxidized vegetable oil or derivates into biobased carbonated materials. The different catalytic systems have been discussed and compared in terms of catalytic performance, employed substrates, and reaction conditions.

Chemical fixation of CO2 with epoxides catalyzed by DBO as activator for the LiI promoted system: A theoretical study

Chemical fixation of carbon dioxide into value-added products is a promising idea. However, its conversion to valuable organic compounds requires highly efficient and safe catalytic system. In this work, the catalytic efficiency of the nontoxic organic base 1, 4‑Diazabicyclo Oct-4-ene (DBO) and its improved result after it has been cooperated with LiI salt have been studied. We gained more insight into the catalytic effects of DBO/LiI on the fixation of CO2 by means of density functional theory calculations using exchange–correlation functional B3LYP through basis sets of LANL2DZ for iodine and 6–31 + G(d,p) for non-iodine atoms. The calculations were carried out in both gas phase and in the presence of water as a solvent. Two reaction mechanisms were proposed and their respective energy was investigated to identify the favorable path for DBO/LiI system catalyzed reaction. Mechanism I is more favorable, in which the ring-opening of epoxide is the rate-limiting step which demands 32.20 kcal mol−1 Gibbs free energy of activation in the gas phase and 20.60 kcal mol-1in water. Lastly, this work validates that DBO in the presence of LiI displayed better catalytic activity for the title reaction and water is a good solvent for DBO/LiI catalyzed cycloaddition of CO2 with an epoxide.

Catalytic performance of MOFs containing trinuclear lanthanides clusters in the cycladdition reaction of CO2 and epoxide

With the rapid development of global industrialization, global warming and ocean acidification caused by the accumulation of greenhouse gases (such as CO2) have attracted widespread attention. It is of great significance to use microporous metal-organic frameworks (MOFs) to adsorb carbon dioxide and further convert it into valuable chemical products. Herein, two kinds of isomorphic (MOFs): {[Ln3(deta)2(DMF)2(COOH)·2H2O]·DMF·H2O}n (LnDy(1), Tb(2), DMF = N-N-dimethyl formamide) based on 4-(3,5-dicarboxyphenoxy)phthalic acid (H4deta) ligands were successfully synthesized by the solvothermal synthesis method. Interestingly, MOFs 1–2 is based on a trinuclear Dy/Tb unit connected to six adjacent trinuclear Dy/Tb units via a (deta)4- ligand, extending to a 3D microporous network structure. MOFs 1–2 not only has good thermal stability, chemical stability and excellent water resistance, but also has abundant active sites of Lewis acid due to the fact that the metal center of MOFs 1–2 is lanthanides metal. The results show that MOFs 1–2 has a good catalytic activity for the chemical fixation of carbon dioxide with epoxides under moderate conditions. Moreover, they can be recycled at least 5 times without affecting their activity, showing excellent chemical stability and reusability. In addition, the reaction mechanism of CO2 cycloaddition to PO catalyzed by MOF 1–2 was also discussed.

Rational design of Cu(I)-anchored porous covalent triazine framework (CTF) for simultaneous capture and conversion of CO2 at ambient conditions

The selective carbon capture and utilization (CCU) as a C1 source is sought to be an important step towards environmental remediation and sustainable production of useful chemicals. In this context, herein, we report the strategic integration of noble metal-free Cu(I) catalytic sites with a nitrogen-rich, CO2-philic, bipyridine functionalized covalent triazine framework (bipy-CTF) by a post-synthetic approach. The Cu(I)@bipy-CTF showed very good performance for simultaneous capture and fixation of CO2 into α-alkylidene cyclic carbonates (α-aCCs), high-value commodity chemicals at ambient conditions. Further, the Cu(I) anchored bipy-CTF showed high CO2 affinity with the interaction energy of 44.09 kJ/mol attributed to the presence of CO2-philic, basic nitrogen sites. The presence of both CO2-philic nitrogen and alkynophilic Cu(I) sites decorated in the 1D channels of bipy-CTF provided a good catalytic activity for the chemical fixation of carbon dioxide from dilute gas (13 % CO2) to yield α-aCCs at atmospheric pressure (balloon) of CO2. Notably, Cu(I)@bipy-CTF showed high recyclability and chemical stability for multiple catalytic cycles. Overall, the present work represents a rare example of a COF-based recyclable catalyst for CO2 fixation from dilute gas into valuable chemicals under mild conditions.

Single Crystal Copper and Gold Alloys for the Plasmonically Enhanced CO2 Reduction Reaction

Chemical fixation of carbon dioxide (CO2) into chemical fuels has raised a lot of interest due to its role in removing greenhouse gasses from the atmosphere to store them as a potential source of energy. CO2 removal techniques have been widely studied and are of great interest because they can be used synergistically as a low-cost source of carbon to supplement and support the existing chemical synthesis of feedstocks and hydrocarbon fuels. One of the most common approaches to the remediation of atmospheric CO2 is the electrochemical reduction of CO2. We have been studying the formation of copper (Cu) films and its alloys with gold (Au). Metal alloys have been shown to exhibit interesting properties to enhance chemical processes beyond those of their individual components, improving the applications in the plasmonic and catalysis fields.Cu and Au are both excellent plasmonic and catalytic materials that show tunable optical properties, strong absorptions in the visible and near infrared, and catalytic activity. However, the applications of Cu materials alone are limited due to Cu’s chemical instability and tendency to oxidation, which inhibits their plasmonic properties and reduces their catalytic performance. By alloying Cu with Au, we have overcome copper’s chemical instability and improved the catalytic properties due to synergistic effects.As a result of our studies, we have also developed a method to deposit Cu2O single crystal film, a material that exhibits semiconductor properties and opens a new line of opportunities for plasmonic applications. In this poster, we will show an overview of our results and discuss the potential applications to plasmonic electrocatalysis and sensors.

Novel and sustainable carboxylation of terminal alkynes and CO2 to alkynyl carboxylic acids using triazolium ionic liquid-modified PMO-supported transition metal acetylacetonate as effective cooperative catalysts.

Efficient and sustainable chemical fixation of CO2 into value-added chemicals is one of the most promising objectives in environmental chemistry. In this work, transition metal acetylacetonate immobilized onto triazolium ionic liquid-modified periodic mesoporous organosilica PMO-IL-M(x) was successfully prepared and investigated as an effective and heterogeneous catalyst in the direct carboxylation of terminal alkynes and CO2 to the desired alkynyl carboxylic acids. It was found that the catalyst PMO-IL-Sn(0.3) exhibited extraordinary catalytic performance in terms of excellent activity, stability, productivity, and excellent yields under mild reaction conditions. Moreover, the catalyst PMO-IL-Sn(0.3) could be easily recovered and reused at least six times without considerable loss in catalytic activity. This work provides a sustainable and efficient synergistic strategy for the chemical fixation of carbon dioxide into valuable alkynyl carboxylic acids.

Novel and high efficient cycloaddition of CO2 with epoxides to cyclic carbonates over reusable mesoporous KIT-6 supported imidazolium lactate catalyst

ABSTRACT. A series of mesoporous KIT-6 supported ionic liquids were prepared and tested as effective and practical catalysts for the synthesis of cyclic carbonates by the cycloaddition of CO2 with epoxides. The effects of type of catalysts, catalyst amount, CO2 pressure, reaction temperature and catalyst stability have also been investigated in detail, the catalyst KIT-6@ILCH3CH(OH)COO(0.6) exhibited excellent activity in good to excellent yields, may be attributed to the synergetic effect between hydroxyl groups and lactate anion of the ionic liquid. In addition, the supported catalyst can be easily recovered and reused for six times still with satisfactory catalytic activity. Moreover, a general synergetic catalytic mechanism for the reaction was proposed. This work introduces a new and highly efficient pathway to explore the supported ionic liquids for the chemical fixation of carbon dioxide.
 
 KEY WORDS: Mesoporous KIT-6, Ionic liquid, High efficient, Carbon dioxide, Cyclic carbonates, Recyclable catalyst
 
 Bull. Chem. Soc. Ethiop. 2022, 36(2), 433-450. 
 DOI: https://dx.doi.org/10.4314/bcse.v36i2.16

Nitrogen-rich dual linker MOF catalyst for room temperature fixation of CO2 via cyclic carbonate synthesis: DFT assisted mechanistic study

The benign synthesis of a novel Zn based Lewis acid-base bifunctional metal-organic framework (ITH-1) and its room temperature catalytic ability for the chemical fixation of carbon dioxide via cyclic carbonate synthesis is reported herein. ITH-1 is characterized by the presence of mono coordinated pendant imidazole groups throughout the framework inducing Lewis basicity. The synthesized material is crystallized in the monoclinic space group as revealed by the Single Crystal X-ray Diffraction Analysis and possesses a 2 D non-planar interdigitated network wherein the neighbouring sheets are connected via strong hydrogen bonding (1.947 Å). ITH-1 was characterized thoroughly via various physicochemical analyses such as XRD, FT-IR, Raman, FE-SEM, CHN, ICP, TGA and was found thermally stable up to 300 ⁰C. The co-existence of accessible and active Lewis acid (Zn) –Lewis base (imidazole) moieties rendered ITH-1 the potential to catalyse the cycloaddition of CO2 with propylene oxide under solvent and co-catalyst free conditions (~95% conversion) at moderate temperatures with remarkable reusable performance (over 5 times). ITH-1 manifested excellent CO2 conversion even under room temperature and 1 bar pressure in the presence of a co-catalyst. Density Functional Theory (DFT) calculations utilizing M06 functional were exercised to envisage the mechanism behind the successful CO2 conversion by ITH-1 at room temperature and were found to be in clear agreement with the experimental results.

Recent Progress on N‐heterocyclic Carbene Catalysts in Chemical Fixation of CO2

AbstractN‐heterocyclic carbene and related complexes are a class of catalysts with excellent catalytic activity which are widely used in the chemical fixation of carbon dioxide. This review focuses on the application of a carbene‐metal catalytic system, carbene‐free‐metal catalytic system and synergistic catalytic technology of various technologies in the conversion of carbon dioxide. The possible role of carbene materials in chemical carbon fixation is discussed by analyzing several types of typical chemical carbon fixation mechanisms.

“Spring-loaded” mechanism for chemical fixation of carbon dioxide with epoxides

Carbon dioxide (CO2) fixation into valuable chemicals is of great significance, but a molecular level rational design of catalysts remains a challenge. Herein, based on the proposal of a “spring-loaded” mechanism, a family of phenolic hydroxyl imidazolium salt-based ionic liquids was designed for CO2 cycloaddition with epoxides into cyclic carbonates. The cation-anion interaction intensity was finely modulated through tailoring the position of the hydroxyl group. The moderate intensity endows superior nucleophilic leaving ability of the I− anion to provide strong C···I interaction for the rate-determining ring-opening step. The synergy of nucleophilic attack by the I− anion, electrophilic attack by a hydroxyl group, and corresponding stabilization effect enabled a high yield within a short reaction time, even at room temperature and atmospheric conditions. A volcano-type regulation of the spring-loaded mechanism was unraveled, revealing the crucial parameter in the designation of high-performing catalyst for CO2 transformation via cycloaddition.