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Energy profiles describing stages 1 and 2 of PC formation catalyzed by ZnBr2 and ionic liquid catalysts (tetra-n-butylammonium chloride and tetra-n-butylammonium lauryl sulfate). Arrows show directions of the considered chemical reactions
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![Thermogram of [bmim][C12ESO4]](publication/320406524/figure/fig3/AS:941522958696456@1601487974910/Thermogram-of-bmimC12ESO4_Q320.jpg)
CO2 capture is an efficient possibility to mitigate environmental impacts. An efficient transformation of CO2 into useful chemicals is a need from environmental protection and resource utilization viewpoint. Cyclic carbonates, such as propylene carbonate is used in numerous technologies. We hereby report eight surface active ionic liquids (SAILs) c...
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Chemical conversion of carbon dioxide (CO2) to value-added useful chemicals like cyclic carbonates represents one potential solution to climate warming. Here, a kind of porous organic polymer (HAT-TP) with large surface area and excellent carbon dioxide uptake capacity is prepared via a condensation reaction to introduce hexaazatriphenylene (HAT) u...
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... In addition, CO 2 is a thermodynamically stable molecule needing harsh conditions for chemical transformations to occur. [6][7][8][9] On the other hand, methane (CH 4 ) is the main product derived from the uncontrolled degradation of biomass. 10 In open dumps and landfills, the chemical composition of the landfill gas generated by the decomposition of solid urban waste is basically CH 4 (60%) and CO 2 (40%). ...
One of the main causes of climate change is the increased concentration of greenhouse gases from anthropogenic sources. Therefore, the search for processes that provide mitigation of these gases is imperative and very important. Dry reforming of methane (DRM) is a process that converts CO2 and CH4 in pure syngas. Thus, this study aims to evaluate the influence of the calcination temperature (500 and 700 °C) in the titanate nanotubes (TNT) structure. The calcination at 700 °C led to a new morphology in the form of titanate nanorods (TNR). TNT and TNR nanostructures were modified with Ni and used as catalysts in the DRM reaction. The CO2 and CH4 conversions were around 60 and 48%, respectively, when using Ni-TNT500 at 700 ºC, while values around 85 and 70%, respectively, were obtained using TNR in the same reactional condition. Both catalysts presented values of H2/CO ratio near 1.
... The fascinating field of surface chemistry is to study the thermodynamic properties and micellar behavior of amphiphilic compounds known as surfactants [1,2]. Surfactants have been extensively utilized in diverse fields as bio-imaging agents [3], template for material synthesis [4], lubricants [5], metal ion extraction [6], drug and genes delivery [7], gene therapy [8], micellar catalysis [9], wood preservative [10], detergency [11], corrosion inhibitors [12], solubilization and formulations of medicines [13], oil/petroleum recovery [14], emulsions stabilizer [15], catalytic conversion of CO 2 [16] etc. Existences of both polar/apolar parts are responsible to form aggregates (spherical/nonspherical, microtubules, vesicles, bilayered structures etc.) above certain concentration known as critical micellar concentration (CMC). Also, they have potential to reside at the interface, hence decrease the surface tension of liquids by improving their wetting and spreading qualities. ...
An investigation has been carried out to gain insight of the micellization behavior of streptomycin sulfate, a surface-active drug, in aqueous medium for six amino acids (proline, glutamic acid, asparagine, glycine, histidine, and aspartic acid) at 0.01 mol·kg⁻¹. The thermodynamic aspects were analyzed using three techniques: conductivity, density, and speed of sound measurements at various temperatures (293.15–313.15 K) along with UV–Vis spectroscopy at a specific temperature of 298.15 K. By employing conductometry, valuable data on micellization and the degree of ionization of the drug were obtained. The impact of amino acids on two essential parameters, the critical micellar concentration (CMC) and thermodynamic aspects of drug micellization, have been examined. Interestingly, the presence of amino acids was found to enhance the drug tendency to form micelles, as depicted by the CMC variations. The study also investigated the suitability of UV–Vis spectroscopy with pyrene as a probe to explore the interactions between amino acids and the drug. Further, density and speed of sound analysis provides information about strong interactions in streptomycin sulfate-amino acids-water system. The results revealed significant changes in the micropolarity and micelle assembly due to these interactions in aforesaid system.
Graphical Abstract
... Dodecyl benzene sulfonate (abbreviation as DBS) based anionic ionic liquid surfactants can be prepared from metathesis of common imidazolium ionic liquids (such as 1-ethyl-3methylimidazolium chloride, 1-butyl-3-methylimidazolium chloride) and sodium dodecyl benzene sulfonate (SDBS). Synthesis, aggregation behavior, and catalysis property of 1-butyl-3-methylimidazolium dodecyl benzene sulfonate ([Bmim][DBS]) were investigated [10,[44][45][46]. ...
Ionic liquid surfactant (ILS) shows potential application in surfactant foam enhancing oil recovery (SFEOR). The structure–activity relationship between structural characteristics and foam feature is vital for the design and selection of favorable ILS for SFEOR. In this paper, the effect of structural substituent groups of anionic ILSs on foam features was established from experimental methods and Density functional theory (DFT) simulations. Physicochemical features of two anionic ILSs, 3-butyl-1-ethoxycarbonylimidazolium dodecyl benzene sulfonate ([Etbim][DBS]) and 1-butyl-3-butylcarbonylimidazolium dodecyl benzene sulfonate ([Btbim][DBS]) was determined. By surface tensiometry, the critical micelle concentration (CMC) values of [Etbim][DBS] and [Btbim][DBS] were 0.324 mmol/L and 0.211 mmol/L respectively. Foam characteristic of two ILSs were studied, whose tendency followed: [Etbim][DBS] > [Btbim][DBS]. ILS hydrates showed tendency: [Etbim][DBS] (H2O)n < [Btbim][DBS] (H2O)n. Binding energy (D0) values followed the tendency: [Etbim][DBS] (H2O)n > [Btbim][DBS] (H2O)n. Experimental and DFT results verified the introduction of longer ester alkyl chain length in imidazolium cation was adverse to foam features of ILSs. This information will help to screen new foam surfactants for SFEOR.
... Plenty of organic, inorganic, and hybrid materials are being steadily developed to interact with CO2. [9][10][11][12][13][14][15] Physical and chemical sorbents aiming to fix CO2 exhibit very different sets of physicochemical properties and thermodynamics of adsorption. Due to the versatility of the foreseen CO2 scavenging applications, there is no single criterion according to which the elaborated sorbents and CCS technologies can be rated. ...
Large-scale applications are waiting for an optimal CO2 scavenger to reinforce CCS and CCU technologies. We herein introduce and succinctly validate a new philosophy of capturing gaseous CO2 by negatively-charged carbonaceous structures. The chemical absorption of CO2 turns out possible thanks to the emergence of significant nucleophilic interaction carbon centers upon applying voltage. The carbonaceous cathode, therefore, may serve as a prototype of a new CO2 sorbent. As a model to simulate chemisorption, we used a small-sized graphene quantum dot (GQD). According to the recorded reaction profiles, the negatively charged GQD containing 16 carbon atoms readily reacts with the CO2 molecule and produces carboxylated GQD. In turn, the activation energy (60 kJ/mol) and energy effect ( 55 kJ/mol) for the reaction in water appeared surprisingly competitive in the context of the literature. We hypothesize that the carbonaceous cathode deserves in-depth experimental research as a possible CO2 chemical sorbent. Despite we used GQD for simulations, the encouraging results can be extrapolated to other nanoscale carbons and, more importantly, to the activated carbon species widely employed in modern electrochemical devices.
... Furthermore, the ionic behavior of these materials can stabilize the catalytic species and intermediates [106,107]. Moreover, the ILs themselves have been used as the catalyst in a variety of reactions, from biodiesel production, to CO 2 conversion [108][109][110]. In some studies, ILs acted as both a solvent and a catalyst simultaneously [111]. ...
Innovation in materials specially formulated for additive manufacturing is of great interest and can generate new opportunities for designing cost-effective smart materials for next-generation devices and engineering applications. Nevertheless, advanced molecular and nanostructured systems are frequently not possible to integrate into 3D printable materials, thus limiting their technological transferability. In some cases, this challenge can be overcome using polymeric macromolecules of ionic nature, such as polymeric ionic liquids (PILs). Due to their tuneability, wide variety in molecular composition, and macromolecular architecture, they show a remarkable ability to stabilize molecular and nanostructured materials. The technology resulting from 3D-printable PIL-based formulations represents an untapped array of potential applications, including optoelectronic, antimicrobial, catalysis, photoactive, conductive, and redox applications.
... 11 Room-temperature ionic liquids and their task-specific derivatives constitute a promising group of CO 2 adsorbents. [12][13][14][15][16][17][18][19][20][21][22][23] Esperanca and coauthors 24 proposed an elegant design of magnetic ionic liquids in combination with metalorganic scaffold composites. The resulting structures turned out to contain numerous microscale pores. ...
The development of robust carbon dioxide (CO2) scavengers is a challenging but paramount problem of modern humanity. In the present work, we report a prospective CO2 sorbent based on amino-functionalized graphene (FG). Amino-FG retains the favorable physicochemical properties of graphene and acquires the capability of chemically fixing CO2via the carbamic acid formation mechanism. In the present work, we comprehensively investigate CO2 capturing prospects by extensively amino-FG using hybrid density functional theory. We show that up to six amino groups can be grafted, remain stable, and subsequently chemisorb CO2 per benzene ring. Two functional groups above the benzene ring and four such groups below the benzene ring represent a thermodynamically stable molecular configuration in which the number of carbon atoms is equal to the number of functional groups. The thermochemistry of chemisorption is, in general, negatively impacted by the increase in the density of functional groups. However, a less favorable Gibbs free energy is compensated by a several fold higher number of prospective reaction sites. The thermochemistry results are rationalized by considering steric hindrances on the surface of graphene in the context of the states of hybridization and genuine geometries of the amino- and carboxamido functional groups. The functionalization and chemisorption decrease the hydrophobicity of graphene derivatives and, therefore, foster the development of novel and more robust chemical engineering setups.
... As an alternative, the transesterification between EC and alcohols can not only be performed under mild conditions, but also linear organic carbonates and ethylene glycol can be produced by the reaction (Scheme 1, b). Furthermore, this route is also regarded as an indirect utilization of CO 2 because EC as reactant can be synthesized by the reaction of CO 2 with epoxide or ethylene glycol [20,21]. Many catalysts have been used to catalyze the transesterification between EC and alcohols, such as metal oxides [22][23][24][25][26][27], alkali metal hydroxides [28], alkali metal salts [29], anion exchange resins [30], hydrotalcite [31], sodium bauxite [32], montmorillonite [33], and polymers [34]. ...
A series of bisimidazolium tungstate ionic liquids were synthesized and applied to catalyze the reaction of ethylene carbonate (EC) with alcohols. A detailed investigation was carried out on the relationship between catalyst structures and catalytic activities. The result showed that 1-butyl-3-methyl-bisimidazolium tungstate ([Bmim]2WO4) containing double C2–H in bisimidazolium and WO4²⁻ had more effectively catalytic performance than other bisimidazolium tungstate and conventional imidazolium salt (OAc⁻, Cl⁻, Br⁻). Under the optimized conditions of 1:15 molar ratio of EC and ethanol, 5 mol% [Bmim]2WO4, 85 °C and 0.5 h, the yield of diethyl carbonate (DEC) was nearly 100%. The detailed DFT calculations and NMR spectroscopy indicated that the high catalytic activity of [Bmim]2WO4 was not only because the strong nucleophilic ability of WO4²⁻ could activate ethanol, but also the special structure of double C2–H in bisimidazolium could cooperatively activate EC. The reaction was catalyzed by synergistic effect in double C2–H and WO4²⁻ of [Bmim]2WO4. In addition, [Bmim]2WO4 could be used seven times without significant loss of catalytic activity.
Graphical Abstract
... Activation of CO 2 can be accomplished through reduction routes (Francke et al., 2018;Melchionna et al., 2021) in which desirable products are carbon monoxide, formic acid, methanol, methane, or > C2 species (Albero et al., 2020). Alternatively, carbon dioxide can be exploited in cyclic carbonates or heterocycle formation (North et al., 2010;Fiorani et al., 2015;Yu and He, 2015;Guo et al., 2021;Vieira et al., 2018Vieira et al., , 2019Faria et al., 2021) or as a single-carbon-atom building block for its fixation into organic compounds (Liu et al., 2015;Cao et al., 2018;Cherubini-Celli et al., 2018;Tlili and Lakhdar, 2020;Zhang et al., 2020;Sahoo et al., 2021;Yuan et al., 2021;He et al., 2020) upon creation of new C-C or C-heteroatom bonds. Mechanistically, these processes can be accomplished through 1) the reduction of carbon dioxide to its radical anion, followed by its reaction with the organic scaffold (in dimethylformamide, E 0 (CO 2 /CO 2 •-) −2.21 V vs. saturated calomel electrode, SCE, corresponding to −1.97 V vs. standard hydrogen electrode) (Lamy et al., 1977;Otero et al., 2006;Berto et al., 2015) or 2) upon the formation of reduced intermediates of the organic substrate accomplished through chemical, electrochemical, or photochemical routes and their subsequent reactivity with CO 2 (Yuan et al., 2021). ...
The utilization of carbon dioxide as a raw material represents nowadays an appealing strategy in the renewable energy, organic synthesis, and green chemistry fields. Besides reduction strategies, carbon dioxide can be exploited as a single-carbon-atom building block through its fixation into organic scaffolds with the formation of new C-C bonds (carboxylation processes). In this case, activation of the organic substrate is commonly required, upon formation of a carbanion C⁻, being sufficiently reactive toward the addition of CO2. However, the prediction of the reactivity of C⁻ with CO2 is often problematic with the process being possibly associated with unfavorable thermodynamics. In this contribution, we present a thermodynamic analysis combined with density functional theory calculations on 50 organic molecules enabling the achievement of a linear correlation of the standard free energy (ΔG⁰) of the carboxylation reaction with the basicity of the carbanion C⁻, expressed as the pKa of the CH/C⁻ couple. The analysis identifies a threshold pKa of ca 36 (in CH3CN) for the CH/C⁻ couple, above which the ΔG⁰ of the carboxylation reaction is negative and indicative of a favorable process. We then apply the model to a real case involving electrochemical carboxylation of flavone and chalcone as model compounds of α,β-unsaturated ketones. Carboxylation occurs in the β-position from the doubly reduced dianion intermediates of flavone and chalcone (calculated ΔG⁰ of carboxylation in β = −12.8 and −20.0 Kcalmol⁻¹ for flavone and chalcone, respectively, associated with pKa values for the conjugate acids of 50.6 and 51.8, respectively). Conversely, the one-electron reduced radical anions are not reactive toward carboxylation (ΔG⁰ > +20 Kcalmol⁻¹ for both substrates, in either α or β position, consistent with pKa of the conjugate acids < 18.5). For all the possible intermediates, the plot of calculated ΔG⁰ of carboxylation vs. pKa is consistent with the linear correlation model developed. The application of the ΔG⁰ vs. pKa correlation is finally discussed for alternative reaction mechanisms and for carboxylation of other C=C and C=O double bonds. These results offer a new mechanistic tool for the interpretation of the reactivity of CO2 with organic intermediates.
... Especially, metalcontaining ionic liquids have been successfully used as catalysts in catalytic synthesis, which combine the advantages of both ionic liquid and transition metal catalysis and often leading to improved catalytic performance comparing to the classical ionic liquids [31,32]. In this respect, many ILs including metal-containing ILs have been synthesized and they exhibited good catalytic performance in the transformation of CO 2 into cyclic carbonates [33][34][35][36][37]. Despite these advances, these catalytic systems often suffer from some disadvantages such as ILs separation and recyclability. ...
In the present study, we demonstrated the synthesis of copper oxychloride anionic benzotriazolium ionic liquid-modified periodic mesoporous organosilica PMO@ILCu2(OH)3Cl2(x) as efficient and green retrievable heterogeneous nanocatalysts for the synthesis of cyclic carbonates via cycloaddition of CO2 with epoxides. Compared to other nanocatalysts, a superior catalytic activity was observed with PMO@ILCu2(OH)3Cl2(1.0), giving excellent yields and selectivities under solvent- and cocatalyst-free conditions. We also found that the existence of intensification synergistic effects from the hydroxyl groups sites of periodic mesoporous organosilica and the active sites of the functionalized ionic liquid, resulting in the enhanced catalytic activity. The catalytic process displayed ease of recovery, excellent stability and recyclability for at least five runs without significant loss of its catalytic activity. The developed catalytic system is proven to be a powerful tool for the chemical fixation of CO2 with epoxides to produce the cyclic carbonates.
Graphical abstractAn efficient protocol is described for producing cyclic carbonates in excellent yields and selectivities under cocatalyst- and solvent-free conditions by treating epoxides with carbon dioxide, promoted by copper oxychloride anionic benzotriazolium ionic liquid-modified periodic mesoporous organosilica.
... Surface-active ionic liquids (SAILs) consisting of the known cations 1-butyl-3-methylimidazolium ([bmim + ]) and tetra-n-butylammonium ([TBA + ]), as well as longchain anions: lauryl sulfate ([C 12 [59,60]. Due to its higher molecular volume, which increases the distance between the cation and the anion, and weakening the electrostatic interaction leading to a more electrophilic cation, [TBA + ] proved to be more active as a catalyst. ...
The current production of organic cyclic carbonates involves the reaction of appropriate alcohols with toxic phosgene. But an alternative route for obtaining these valuable products is the cycloaddition reaction of CO 2 with appropriative epoxides. The development of new catalytic systems for this reaction is a highly active field of research works. For this purpose, were developed many effective catalytic systems, such as organocatalysts, metal-organic frameworks, homogeneous metal-based catalysts, and ionic liquid catalysts. Among them, zinc-containing and ionic liquid catalysts are highly active systems, resulting in the increase in selectivity and the beneficial effect on the reaction rate under mild reaction conditions: reaction temperatures of below 100 °C at a low CO 2 concentration and pressure at 0.1 MPa, if possible, without solvents and co-catalysts. This review article summarizes and discusses the results of research works over the last 10-15 years on the study of the homogeneous zinc-containing and ionic liquid catalysts for the cycloaddition reaction of CO 2 with epoxides. We hope that it can be stimulated for further development in this area and will be useful for understanding the potential commercialization of these catalysts.
