Ammonium-, phosphonium- and sulfonium-based 2-cyanopyrrolidine ionic liquids for carbon dioxide fixation

Chaban, Vitaly V.; Andreeva, Nadezhda A.; Voroshylova, Iuliia V.

doi:10.1039/d2cp00177b

Cited by 14 publications

(8 citation statements)

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“…This driving force is not strong enough and much less than that for the formation of the carboxylic product with [MN] (ΔH = −35.33 kJ mol −1 ), leading to inferior CO 2 uptake capacity (0. 35 reported for organic solvents such as DMSO, 32 but our work shows that the IL provides a more concentrated and nonvolatile medium for CO 2 capture. In addition, the cations and the −CN groups have also been found to be helpful in interacting with CO 2 .…”

Section: ■ Results and Discussionmentioning

confidence: 58%

“…For STSILs in CO 2 chemisorption, besides the anion-involved reaction pathway, CO 2 capture could also be achieved via nucleophilic attack of the basic anion on the alkyl chains in the cation through the ylide formation pathway, which has been demonstrated both experimentally and theoretically. ,− We examined the possibility of this reaction mechanism in the [MN]-derived STSILs upon reacting with CO 2 by DFT (Figure S18). The cation (tetraethylphosphonium, [P 2222 ]) was included and an ion pair model was used to compare the three different reaction mechanisms of CO 2 chemisorption (Figure S18A).…”

Section: Resultsmentioning

confidence: 99%

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CO₂ Chemisorption Behavior in Conjugated Carbanion-Derived Ionic Liquids via Carboxylic Acid Formation

Suo

Do‐Thanh

et al. 2022

J. Am. Chem. Soc.

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Superbase-derived task-specific ionic liquids (STSILs) represent one of the most attractive and extensively studied systems in carbon capture via chemisorption, in which the obtained CO2 uptake capacity has a strong relationship with the basicity of the anions. High energy input in desorption and side reactions caused by the strong basicity of the anions are still unsolved issues. The development of other customized STSILs leveraging an alternative driving force to achieve efficient CO2 chemisorption/desorption is highly desirable yet challenging. In this work, carbanion-derived STSILs were developed for efficient CO2 chemisorption via a carboxylic acid formation pathway. The STSIL with the deprotonated malononitrile molecule ([MN]) as the anion exhibited much higher CO2 uptake capacity than the one derived from 2-methylmalononitrile ([MMN]). Notably, this trend was opposite to their basicity ([MN] < [MMN]). Detailed characterization of the products, supported by density functional theory simulations of spectra and calculations of the reaction energetics, demonstrated that carboxylic acid was formed upon reacting with CO2 via proton transfer in [MN]-derived STSILs but not in the case of [MMN] due to lack of an α-H. The preference of the carboxylic acid product over carboxylate formation was driven by the extended conjugation among the central sp2 carbon, the as-formed carboxylic acid, and the two nitrile groups. The achievements made in this work provide an alternative design principle of STSILs by leveraging the extended conjugation in the CO2-integrated product.

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Section: ■ Results and Discussionmentioning

confidence: 58%

Section: Resultsmentioning

confidence: 99%

CO₂ Chemisorption Behavior in Conjugated Carbanion-Derived Ionic Liquids via Carboxylic Acid Formation

Suo

Do‐Thanh

et al. 2022

J. Am. Chem. Soc.

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“…The phosphonium-based RTILs paired with aprotic anions form both a carbamate product out of the anion and a carboxyl product out of the cation. Therefore, 2 mol of CO 2 per 1 mol of the RTIL can be bound at a time. , …”

Section: Introductionmentioning

confidence: 99%

“…The phosphonium ylide is an important intermediate in the CO 2 chemisorption by the tetraalkylphosphonium-based RTILs. The ylide is a neutral compound that forms reversibly at above 333 K in the case of the chemisorption reaction of tetraalkylphosphonium-based RTILs with carbon dioxide. , The presence of CO 2 in the system favors the formation of ylide. Compared to the current industrial-scale technology that employs aqueous monoethanolamine solutions, the finely tuned RTILs can substantially decrease the energy demands.…”

Section: Introductionmentioning

confidence: 99%

“…Therefore, 2 mol of CO 2 per 1 mol of the RTIL can be bound at a time. 23,37 The phosphonium ylide is an important intermediate in the CO 2 chemisorption by the tetraalkylphosphonium-based RTILs. The ylide is a neutral compound that forms reversibly at above 333 K in the case of the chemisorption reaction of tetraalkylphosphonium-based RTILs with carbon dioxide.…”

Section: ■ Introductionmentioning

confidence: 99%

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Carbon Dioxide Chemisorption by Ammonium and Phosphonium Ionic Liquids: Quantum Chemistry Calculations

Chaban

2022

J. Phys. Chem. B

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Carbon capture and storage is an important technological endeavor aiming to improve the ecology by combating global warming. The present work investigates reaction paths that are responsible for CO2 chemisorption by the ammonium- and phosphonium-based ionic liquids containing an aprotic heterocyclic anion 2-cyanopyrrolide. We exemplify that 2 mol of CO2 per 1 mol of the gas scavenger can be theoretically fixed by such ionic liquids. Both the cation and anion participate in the chemisorption. The corresponding standard enthalpies and potential energies are moderately negative. The chemisorption reaction, as revealed by the simulations of competing pathways, is started by the donation of the proton from the cation to the anion. The double covalent bond in the cation’s structure emerges. The barriers to all reactions involving the phosphonium-based cation are relatively small and favor practical applications of the considered sorbents. The performance of the ammonium-based cation is less favorable due to the inherent instability of the tetraalkylammonium ylide. The role of phosphonium ylide in the mechanism of the reaction is carefully characterized. The performance of the aprotic anion as a CO2 scavenger is unaffected by the chemical identity of the counterion. The essential heights of the identified steric barriers underline the necessity to simulate the entire structures of the reacting species to obtain a reliable description of chemisorption. The reported results foster a fundamental understanding of the outstanding CO2 sorption performance of the quaternary ammonium- and phosphonium-based 2-cyanopyrrolides.

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Exploiting process thermodynamics in carbon capture from direct air to industrial sources: The paradigmatic case of ionic liquids

Dorado-Alfaro,

Hospital-Benito,

Moya

et al. 2024

Carbon Capture Science & Technology

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Ammonium-, phosphonium- and sulfonium-based 2-cyanopyrrolidine ionic liquids for carbon dioxide fixation

Abstract: The development of carbon dioxide (CO2) scavengers is an acute problem nowadays because of the global warming problem. Many groups around the globe intensively develop new greenhouse gas scavengers. Room-temperature...

Cited by 14 publications

References 76 publications

CO₂ Chemisorption Behavior in Conjugated Carbanion-Derived Ionic Liquids via Carboxylic Acid Formation

CO₂ Chemisorption Behavior in Conjugated Carbanion-Derived Ionic Liquids via Carboxylic Acid Formation

Carbon Dioxide Chemisorption by Ammonium and Phosphonium Ionic Liquids: Quantum Chemistry Calculations

Exploiting process thermodynamics in carbon capture from direct air to industrial sources: The paradigmatic case of ionic liquids

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Ammonium-, phosphonium- and sulfonium-based 2-cyanopyrrolidine ionic liquids for carbon dioxide fixation

Abstract: The development of carbon dioxide (CO2) scavengers is an acute problem nowadays because of the global warming problem. Many groups around the globe intensively develop new greenhouse gas scavengers. Room-temperature...

Cited by 14 publications

References 76 publications

CO2 Chemisorption Behavior in Conjugated Carbanion-Derived Ionic Liquids via Carboxylic Acid Formation

CO2 Chemisorption Behavior in Conjugated Carbanion-Derived Ionic Liquids via Carboxylic Acid Formation

Carbon Dioxide Chemisorption by Ammonium and Phosphonium Ionic Liquids: Quantum Chemistry Calculations

Exploiting process thermodynamics in carbon capture from direct air to industrial sources: The paradigmatic case of ionic liquids

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CO₂ Chemisorption Behavior in Conjugated Carbanion-Derived Ionic Liquids via Carboxylic Acid Formation

CO₂ Chemisorption Behavior in Conjugated Carbanion-Derived Ionic Liquids via Carboxylic Acid Formation