Ionic Liquid Stabilizes Olefin Facilitated Transport Membranes Against Reduction

Park, Sejoon; Morales‐Collazo, Oscar; Freeman, Benny D.; Brennecke, Joan F.

doi:10.1002/anie.202202895

Cited by 19 publications

(13 citation statements)

References 53 publications

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“…Furthermore, crystalline peaks at 2θ values observed for reduced [Ag + ][NTf 2 – ] and reduced [Ag + ][NTf 2 – ]/[C 10 MIM + ][NTf 2 – ] ILs (Figure b,c) were identical to each other, indicating that the silver(I) ion dissolved in the IL solvent is also reduced to metallic silver by hydrogen gas. These results are in good agreement with a previous FTM study that performed XRD characterization on dark-colored particles produced from reducing [Ag + ][NO 3 – ]/1-hexyl-3-methylimidazolium [NO 3 – ] using hydrogen …”

Section: Resultssupporting

confidence: 92%

“…Metallic silver formed by the hydrogen-promoted reduction of the silver(I) ion in olefin/paraffin separation systems has been characterized by various methods, including color change observation, microscopic analysis, , X-ray photoelectron spectroscopy, and powder XRD analysis. ,, To confirm that the silver(I) ion dissolved in an IL undergoes hydrogen-mediated reduction to metallic silver, neat [Ag + ][NTf 2 – ] and the [Ag + ][NTf 2 – ]/[C 10 MIM + ][NTf 2 – ] IL mixture were both reduced, and the products characterized by powder XRD analysis. Figure S1 in the Supporting Information describes all procedures used to perform in-column silver(I) ion reduction.…”

Section: Resultsmentioning

confidence: 99%

“…Moreover, GC stationary phases containing the 1-decyl-3-methylimidazolium ([C 10 MIM + ]) [NTf 2 – ] IL impregnated with dissolved [Ag + ][NTf 2 – ] were also discovered to mitigate the reduction of silver(I) ion by pure hydrogen carrier gas at temperatures up to 95 °C . These observations are likely due to the presence of multiple [NTf 2 – ] IL anions surrounding the silver(I) ion, resulting in its protection from hydrogen-mediated reduction …”

Section: Introductionmentioning

confidence: 99%

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Deconvoluting the Combined Effects of Gas Composition and Temperature on Olefin Selectivity for Separations Using Silver(I) Ions in Ionic Liquids

et al. 2022

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Silver(I) ions have the propensity of undergoing reduction to form metallic silver within olefin/paraffin separation systems when they are subjected to hydrogen at elevated temperatures. Ionic liquids (ILs) are versatile solvents known for their low vapor pressure, high thermal stability, and structural tunability and have been shown to minimize hydrogen-induced reduction of silver(I) ions when employed as solvents. In the development of robust separation platforms that employ silver(I) ions, it is essential to deploy reliable approaches capable of measuring and assessing the factors that lower the overall separation performance. In this study, silver(I) ions dissolved in an imidazolium-based IL are subjected to mixed gas streams composed of hydrogen, nitrogen, and methane under varying temperatures. Using inverse gas chromatography, a total of 44 columns with stationary phases containing four different concentrations of silver(I) bis[(trifluoromethyl)sulfonyl]imide ([Ag+][NTf2 –]) dissolved in the 1-decyl-3-methylimidazolium ([C10MIM+]) [NTf2 –] IL were used to measure partition coefficients of olefins and paraffins, as well as aromatics, esters, and ketones. Upon exposing the stationary phases to mixed gases at elevated temperatures, olefin partitioning between the silver(I) ion pseudophase and the two other phases (i.e., carrier gas and IL stationary phase) was observed to decrease over time, while partitioning between the IL stationary phase and carrier gas remained unchanged. It was found that exposure gases composed of 5.0 to 85.0 mol % hydrogen and temperatures ranging from 95 to 130 °C resulted in a remarkable acceleration of silver(I) ion reduction and an approximate 36.4–61.3% decrease in olefin partitioning between the silver(I) ion pseudophase and both the carrier gas and IL stationary phase after 60 h. While binary mixtures of hydrogen and nitrogen resulted in a continuous decrease in silver(I) ion–olefin complexation capability, a ternary gas mixture produced varied silver(I) ion reduction kinetics.

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Section: Resultssupporting

confidence: 92%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Deconvoluting the Combined Effects of Gas Composition and Temperature on Olefin Selectivity for Separations Using Silver(I) Ions in Ionic Liquids

et al. 2022

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“…The Journal of Physical Chemistry B compared to nitrate anions. 37 The supported ionic liquid membrane containing 1.7 M Ag + and [C 6 C 1 Im][NTf 2 ] maintained a selectivity of 8.2 ethylene to ethane for the duration of a 7 day process.…”

Section: ■ Introductionmentioning

confidence: 99%

Insights into the Absorption of Hydrocarbon Gases in Phosphorus-Containing Ionic Liquids

et al. 2023

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The solubility of ethane, ethylene, propane, and propylene was measured in two phosphorus-containing ionic liquids, trihexyltetradecylphosphonium bis(2,4,4-trimethylpentyl)phosphinate, [P 6,6,6,14 ][DiOP], and 1butyl-3-methylimidazolium dimethylphosphate, [C 4 C 1 Im][DMP], using an isochoric saturation method. The ionic liquid [C 4 C 1 Im][DMP] absorbed between 1 and 20 molecules of gas per 1000 ion pairs, at 313 K and 0.1 MPa, while [P 6,6,6,14 ][DiOP] absorbed up to 169 molecules of propane per 1000 ion pairs under the same conditions. [C 4 C 1 Im][DMP] had a higher capacity to absorb olefins than paraffins, while the opposite was true for [P 6,6,6,14 ][DiOP], with the former being slightly more selective than the later. From the analysis of the thermodynamic properties of solvation, we concluded that in both ionic liquids and for all of the studied gases the solvation is ruled by the entropy, even if its contribution is unfavorable. These results, together with density measurements, 2D NMR studies, and self-diffusion coefficients suggest that the gases' solubility is ruled mostly by nonspecific interactions with the ionic liquids and that the looser ion packing in [P 6,6,6,14 ][DiOP] makes it easier to accommodate the gases compared to [C 4 C 1 Im][DMP].

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“…Cycloaddition of CO 2 with epoxides usually undergoes ring opening, CO 2 insertion, and ring closure [37][38][39]. The first step is normally recognized as the rate-determining step and is triggered by an attack by a nucleophilic agent.…”

Section: Introductionmentioning

confidence: 99%

Ordered mesoporous carbon encapsulated linear poly(ionic liquid)s enabling synergy effect of surface groups and ionic moieties for CO2 fixation under mild conditions

Song

et al. 2023

Carb Neutrality

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Carbon dioxide (CO2) fixation into value-added chemicals has attracted growing attention and one promising atom-efficient pathway is via the cycloaddition with three member-ring compounds like epoxides. Herein, we demonstrated that encapsulation of linear poly(ionic liquid)s (PILs) on ordered mesoporous carbon materials provides a facile and feasible approach towards environmental-friendly heterogeneous catalysts with high performance in CO2 cycloaddition with epoxides under mild conditions. A series of novel linear phenolic hydroxyl group functional imidazolium-based PILs synthesized from hydroxymethylation reaction between 4-(imidazol-1-yl)phenol-1-butyl-imidazolium iodide and formaldehyde was loaded on ordered mesoporous carbon FDU-15–600 derived from mesoporous phenolic resin. By virtue of controlling the initial polymerization temperature, the molecular weight of PILs was facilely modulated, reaching strong host–guest interaction during the PIL immobilization. Highly stable immobilized PIL species with spatial satisfaction of ionic moieties and surface groups were thus realized to enable a synergic CO2 conversion via cycloaddition with epoxides. The optimal catalyst exhibited high yield and stable recyclability by using atmospheric CO2 under metal-additive-solvent-free conditions and the activity surprisingly exceeded the corresponding homogeneous parent IL and PIL. Excellent substrate compatibility was found by extending the transformation of more than ten epoxides including the inert ones such as disubstituted cyclohexene oxide. The significantly enhanced activity is attributed to the synergistic effect of the surface hydrogen groups and ionic moieties to accelerate the rate-determining ring-opening process.

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Ionic Liquid Stabilizes Olefin Facilitated Transport Membranes Against Reduction

Cited by 19 publications

References 53 publications

Deconvoluting the Combined Effects of Gas Composition and Temperature on Olefin Selectivity for Separations Using Silver(I) Ions in Ionic Liquids

Deconvoluting the Combined Effects of Gas Composition and Temperature on Olefin Selectivity for Separations Using Silver(I) Ions in Ionic Liquids

Insights into the Absorption of Hydrocarbon Gases in Phosphorus-Containing Ionic Liquids

Ordered mesoporous carbon encapsulated linear poly(ionic liquid)s enabling synergy effect of surface groups and ionic moieties for CO2 fixation under mild conditions

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