Dynamics of Ion Locking in Doubly Polymerized Ionic Liquids

10.26434/chemrxiv.13239059 ◽

2020 ◽

Author(s):

Swati Arora ◽

Julisa Rozon ◽

Jennifer Laaser

Keyword(s):

Dielectric Constant ◽

Ionic Liquid ◽

Ionic Liquids ◽

Ion Pairs ◽

Polymer Chains ◽

Ion Motion ◽

Charged Species ◽

Broadband Dielectric Spectroscopy ◽

Covalently Linked ◽

Insight Into

<div>In this work, we investigate the dynamics of ion motion in “doubly-polymerized” ionic liquids (DPILs) in which both charged species of an ionic liquid are covalently linked to the same polymer chains. Broadband dielectric spectroscopy is used to characterize these materials over a broad frequency and temperature range, and their behavior is compared to that of conventional “singly-polymerized” ionic liquids (SPILs) in which only one of the charged species is attached to the polymer chains. Polymerization of the DPIL decreases the bulk ionic conductivity by four orders of magnitude relative to both SPILs. The timescales for local ionic rearrangement are similarly found to be approximately four orders of magnitude slower in the DPILs than in the SPILs, and the DPILs also have a lower static dielectric constant. These results suggest that copolymerization of the ionic monomers affects ion motion on both the bulk and the local scales, with ion pairs serving to form strong physical crosslinks between the polymer chains. This study provides quantitative insight into the energetics and timescales of ion motion that drive the phenomenon of “ion locking” currently under investigation for new classes of organic electronics.</div>

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Density Functional Theory Study on the Absorption of CO2 by the Ionic Liquid of 1-butyl-3-methylimidazolium Acetate

Advanced Materials Research ◽

10.4028/www.scientific.net/amr.807-809.543 ◽

2013 ◽

Vol 807-809 ◽

pp. 543-548 ◽

Cited By ~ 1

Author(s):

Yan Fei Chen ◽

Yan Hong Cui ◽

Dong Shun Deng ◽

Ning Ai

Keyword(s):

Density Functional Theory ◽

Ionic Liquid ◽

Ionic Liquids ◽

Density Functional ◽

Ion Pairs ◽

Ion Pair ◽

Frontier Molecular Orbitals ◽

Density Functional Theory Study ◽

Electronic Density ◽

Functional Theory

The absorptions of CO2on the 1-butyl-3-methylimidazolium acetate ([Bmi [Ac]) with different substituents are calculated systematically at GGA/PW91 level. Three hydrogen bonds are formed between [A and cations of 1-n-[Bmi [A ([NBmi+) and 1-tert-[Bmi [A ([TBmi+). The interaction between CO2and the [NBmi [A by a C-O bond is much weaker than that with the [TBmi [A by forming a O...O...C...C four member-ring. The chemisorption of CO2on the ion pairs of [NBmi [A is much weaker than that on the [TBmi [A, resulted from the absorption energies analysis. The frontier molecular orbitals shows the electronic density overlap between absorbed CO2and the [A in CO2-[NBmi [A is much weaker than that in [TBmi [A. Therefore, the chemisorption of CO2on the ion pair of [NBmi [A is much weaker than that on the [TBmi [A. The ionic liquids based [NBmi+can be used repetitively, and the adsorbed CO2would be easier desorbed.

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A mechanistic insight into the organocatalytic properties of imidazolium-based ionic liquids and a positive co-solvent effect on cellulose modification reactions in an ionic liquid

RSC Advances ◽

10.1039/c6ra28659c ◽

2017 ◽

Vol 7 (16) ◽

pp. 9423-9430 ◽

Cited By ~ 22

Author(s):

Ryohei Kakuchi ◽

Ryo Ito ◽

Shuhei Nomura ◽

Hadi Abroshan ◽

Kazuaki Ninomiya ◽

...

Keyword(s):

Ionic Liquid ◽

Ionic Liquids ◽

Solvent Effect ◽

Cellulose Modification ◽

Mechanistic Insight ◽

Insight Into

Mechanistic insights into organocatalytic properties of imidazolium-based ionic liquids led to improvements of cellulose modification reactions in ionic liquids.

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Correction: A mechanistic insight into the organocatalytic properties of imidazolium-based ionic liquids and a positive co-solvent effect on cellulose modification reactions in an ionic liquid

RSC Advances ◽

10.1039/c7ra90031g ◽

2017 ◽

Vol 7 (23) ◽

pp. 13876-13876

Author(s):

Ryohei Kakuchi ◽

Ryo Ito ◽

Shuhei Nomura ◽

Hadi Abroshan ◽

Kazuaki Ninomiya ◽

...

Keyword(s):

Ionic Liquid ◽

Ionic Liquids ◽

Solvent Effect ◽

Cellulose Modification ◽

Mechanistic Insight ◽

Insight Into

Correction for ‘A mechanistic insight into the organocatalytic properties of imidazolium-based ionic liquids and a positive co-solvent effect on cellulose modification reactions in an ionic liquid’ by Ryohei Kakuchi et al., RSC Adv., 2017, 7, 9423–9430.

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Simulation of a Solvate Ionic Liquid at a Polarisable Electrode with a Constant Potential

10.26434/chemrxiv.6974636.v1 ◽

2018 ◽

Author(s):

Samuel W. Coles ◽

Vladislav Ivanistsev

Keyword(s):

Boundary Condition ◽

Ionic Liquid ◽

Ionic Liquids ◽

Surface Charge ◽

Computational Studies ◽

Lithium Ions ◽

Liquid Electrode ◽

Constant Potential ◽

Electrode Interface ◽

Insight Into

<div>In this article we discuss the nanostructure and calculated the capacitance of a solvate ionic liquid–electrode interfaces, where the electrode has a constant potential, and is thus inherently polarisable. Lithium ions from the lithium</div><div>glyme solvate ionic liquid are found within 0.5 nm of the electrode at all voltages studied, however, their solvation environment varies with voltage. Our study provides molecular insight into the electrode interface of solvate ionic liquids, with many features similar to pure ionic liquids. A comparison with previous studies of the same electrolyte using the fixed surface charge boundary condition is also illuminating, informing future computational studies of electrolyte–electrode interfaces.</div>

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How Polar Are Ionic Liquids? Determination of the Static Dielectric Constant of an Imidazolium-based Ionic Liquid by Microwave Dielectric Spectroscopy

The Journal of Physical Chemistry B ◽

10.1021/jp053946+ ◽

2005 ◽

Vol 109 (36) ◽

pp. 17028-17030 ◽

Cited By ~ 309

Author(s):

Chihiro Wakai ◽

Alla Oleinikova ◽

Magnus Ott ◽

Hermann Weingärtner

Keyword(s):

Dielectric Constant ◽

Ionic Liquid ◽

Ionic Liquids ◽

Dielectric Spectroscopy ◽

Static Dielectric Constant ◽

Microwave Dielectric

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Recycling of 1,2-Dimethyl-3-propylimidazolium bis(trifluoromethylsulfonyl)imide Ionic Liquid by Stacked Cation and Anion Exchange Adsorption-Desorption

Separations ◽

10.3390/separations6020029 ◽

2019 ◽

Vol 6 (2) ◽

pp. 29

Author(s):

Cynthia A. Corley ◽

Scott T. Iacono

Keyword(s):

Ionic Liquid ◽

Ionic Liquids ◽

Ion Exchange ◽

Anion Exchange ◽

Membrane Separation ◽

Ion Pairs ◽

Exchange Adsorption ◽

Adsorption Desorption ◽

Desorption Method

There are many advantages to using ionic liquids as solvents or catalysts in chemical processes. Their non-volatile characteristic and high cost, however, can pose economic, environmental, and long-term health concerns. As such, the recovery and recycling of ionic liquids have become essential to mitigate their environmental impact and to reduce costs. Numerous recovery and recycling methods have been reported, including distillation, extraction, membrane separation (a.k.a. filtration), adsorption, crystallization, gravity, and electrochemical separation. Whereas most of these methods recover both cations and anions of the ionic liquid as ion pairs, recycling methods such as single-phase ion exchange or mixed-ion exchange/non-ionic adsorption methods recover only one of the ionic liquid ions, typically the cation. These methods are frequently used for the recycling of ionic liquids having simple anions such as chloride or acetate, but are seldom employed for ionic liquids consisting of larger and more complex anions due to the added time and reagent costs necessary for the regeneration of the original ionic liquid. Herein, a combined cation and anion exchange adsorption-desorption method is presented that can effectively separate 1,2-dimethyl-3-propylimidazolium bis(trifluoromethylsulfonimide) [DMPIm][NTf2] ionic liquid from neutral impurities. More importantly, the method is capable of recovery and recycling of the original ionic liquid. Concomitant desorption of both ionic liquid ions was achieved using 0.1 M NaCl: methanol (90:10 v/v) eluent followed by isolation using liquid–liquid extraction to afford high purity products and yields of approximately 60%.

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Insight into conformationally-dependent binding of 1-n-alkyl-3-methylimidazolium cations to porphyrin molecules using quantum mechanical calculations

Physical Chemistry Chemical Physics ◽

10.1039/c9cp01538h ◽

2019 ◽

Vol 21 (19) ◽

pp. 10095-10104 ◽

Cited By ~ 1

Author(s):

Atiya Banerjee ◽

Jindal K. Shah

Keyword(s):

Ionic Liquid ◽

Cytochrome P450 ◽

Ionic Liquids ◽

Binding Energies ◽

Side Chain ◽

Quantum Mechanical ◽

Quantum Mechanical Calculations ◽

Alkyl Side Chain ◽

Catalytic Center ◽

Insight Into

The first step in the biodegradation of imidazolium-based ionic liquids involves the insertion of the –OH group into the alkyl side chain, and it is believed to be triggered by cytochrome P450. In this work, we investigate the effect of conformations on binding energies of ionic liquid cations to the catalytic center of P450.

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Insight into the dispersion behavior of 1-butyl-3-methylimiazolium chloride confined in nanoscale pores of carbon materials

RSC Advances ◽

10.1039/c8ra03033b ◽

2018 ◽

Vol 8 (43) ◽

pp. 24094-24100 ◽

Cited By ~ 3

Author(s):

Shuxia Di ◽

Yiqi Xu ◽

Qunfeng Zhang ◽

Xiaolong Xu ◽

Yuanyuan Zhai ◽

...

Keyword(s):

Ionic Liquid ◽

Ionic Liquids ◽

Liquid Phase ◽

Carbon Materials ◽

Supported Ionic Liquid ◽

Dispersion Behavior ◽

Insight Into

It is important to understand the behaviour of ionic liquids (ILs) in nanoscale pores, as application of supported ionic liquid phase (SILP) materials has attracted much attention.

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