Characterization of the Bridged Proton Structure in HTFSI Acid Ionic Liquid Solutions

Munson, Kyle T.; Vergara, Jason; Yu, Lei; Vaden, Timothy D.

doi:10.1021/acs.jpcb.5b02715

Cited by 17 publications

(15 citation statements)

References 47 publications

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“…3b). 30,31 The ν 1 and ν 3 stretching modes give a very broad band centered at 2920 cm -1 , which overlaps the sharper maximum at 2880 cm 45 Thirdly, DSC measurements revealed a single endothermic peak and a corresponding exothermic peak (see Fig. 4).…”

Section: Synthesis Of [H 3 Omentioning

confidence: 83%

A Hydronium Solvate Ionic Liquid: Facile Synthesis of Air-Stable Ionic Liquid with Strong Brønsted Acidity

Kitada

Takeoka

Kintsu

et al. 2018

J. Electrochem. Soc.

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A new kind of ionic liquid (IL) with strong Brønsted acidity, i.e., a hydronium (H 3 O + ) solvate ionic liquid, is reported. The IL can be described as [H 3 When two or more kinds of substances are mixed, the properties of the mixture can differ from those of the pure substances. Depending on the interactions between the components, some components undergo ionization, e.g. dissociation, protonation, solvation and complexation, due to the neutralization of Brønsted or Lewis acids and bases. Sometimes, the acid-base mixtures can be categorized as ionic liquids (ILs) with melting points below 100• C, which consist only of cations and anions. ILs are regarded as "the third liquid" and some ILs have fascinating physicochemical properties, such as low volatility, low flammability, high chemical, and thermal stability. Furthermore, ILs have received growing interest due to their various uses as media in chemical, biochemical, and/or electrochemical systems. [1][2][3][4][5][6] Common anions of ILs such as BF 4 -, PF 6 -, and AlCl 4 -are produced by neutralization, i.e. the adducts of a Lewis acid (BF 3 , PF 5 , or AlCl 3 ) and a Lewis base (F -or Cl -). Examples of ILs prepared through neutralization include solvate ILs.7-13 Solvate ILs often consist of equimolar molten mixtures of polyethers (linear or cyclic ones, i.e. glymes or crown ethers) and certain metal salts, where the Lewis acidic metal cations are solvated by equimolar amounts of Lewis basic glymes to give complex cations. Besides, neutralization of Brønsted acids and bases produces so-called protic ILs, which are preferred as acid-catalyzed reaction media due to the presence of an acidic proton.3-6 Since proton transfer is a common chemical transformation, Brønsted acidic ILs receive research attention especially for acid catalysts, fuel cells, biomass processing, polymerization, CO 2 fixation, etc.6,14-19 The design of stronger Brønsted acidic ILs and evaluation of the acidity in ILs are important for exploring their possible applications as media for acid-base reactions.Although 21-24 However, there is an exception. In solid, anhydrous HTf 2 N, the proton is bonded to the anion nitrogen and two oxygens of a neighboring HTf 2 N molecule. 25 Likewise, in the case of monohydrate, the imide superacid HTf 2 N remains associated and does not protonate water, as suggested experimentally and theoretically. In the infrared measurements for an H 2 O and HTf 2 N mixture in CCl 4 , strong Fermi resonance for N-H vibrations serves as evidence that HTf 2 N remains * Electrochemical Society Member.z E-mail: kitada.atsushi.3r@kyoto-u.ac.jp intact, and from the ab initio calculations, spontaneous proton dissociation was not observed for the Fig. 1a

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Section: Synthesis Of [H 3 Omentioning

confidence: 83%

A Hydronium Solvate Ionic Liquid: Facile Synthesis of Air-Stable Ionic Liquid with Strong Brønsted Acidity

Kitada

Takeoka

Kintsu

et al. 2018

J. Electrochem. Soc.

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“…Similarly, the worst performer (PEDOT:PMATFSILi80) is the one that swells the least. The swelling behavior of these polymers is mainly due to H‐bonds and electrostatic interactions inherent to the >N ‐ H + moieties coming from TFSI side groups . It should be noted that while the response time should depend on the ionic conductivity of the channel, and hence correlate with the degree of swelling of the conducting polymer film, such correlation is not observed here (Table ).…”

Section: Introductionmentioning

confidence: 99%

Organic electrochemical transistors based on PEDOT with different anionic polyelectrolyte dopants

Inal

Rivnay

Hofmann

et al. 2015

J Polym Sci B Polym Phys

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Recent applications of organic electrochemical transistors (OECTs) in bioelectronics motivate the search for new materials with mixed electronic and ionic conductivity. We investigate the characteristics of a series of poly(3,4‐ethylenedioxythiophene) (PEDOT)‐based materials with a new class of anionic polyelectrolytes used as dopants and stabilizers, replacing the traditionally used poly(styrene sulfonate) (PSS). We show that the backbone of the polyanion plays a major role in determining device performance, while its molecular weight and the counter ion used during PEDOT synthesis play a less important role. We find that transconductance increases with the degree of swelling of the film, consistent with enhanced ion transport. Finally, we identify a polymer that offers performance close to the state‐of‐the‐art. This work highlights the importance of the polyanion phase as a means to control OECT performance. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016, 54, 147–151

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“…HTFSI solutions in PyrrTFSI show very interesting conductivity change behaviors. The solution conductivity increases at lower concentrations and decrease at higher concentrations; a maximum conductivity value can be observed at ~1 M HTFSI [6]. The HTFSI partially ionizes in the solution and a N-H-N "bridged" structure may be formed in the solution, in which a proton is solvated by two TFSI anions.…”

Section: Msa In 04 M and 20 M Htfsi/pyrrtfsimentioning

confidence: 97%

“…In our previous reports, we investigated the properties of a series of acid solutions in ILs such as 3-butyl-1-methylimidazolium tetrafluoroborate (BMIBF 4 ) [3], 3-butyl-1-methylimidazolium bis(trifluoromethanesulfonyl)imide (BMITFSI) [4,5], N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (PyrrTFSI) [6], and 3-ethyl-1-methylimidazolium acetate (EMIOAc) [7]. It has been concluded that the AIL properties strongly depend on the structures of ILs or acids.…”

Section: Introductionmentioning

confidence: 99%

Conductivity, Viscosity, Spectroscopic Properties of Organic Sulfonic Acid solutions in Ionic Liquids

et al. 2019

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Sulfonic acids in ionic liquids (ILs) are used as catalysts, electrolytes, and solutions for metal extraction. The sulfonic acid ionization states and the solution acid/base properties are critical for these applications. Methane sulfonic acid (MSA) and camphor sulfonic acid (CSA) are dissolved in several IL solutions with and without bis(trifluoromethanesulfonyl)imine (HTFSI). The solutions demonstrated higher conductivities and lower viscosities. Through calorimetry and temperature-dependent conductivity analysis, we found that adding MSA to the IL solution may change both the ion migration activation energy and the number of “free” charge carriers. However, no significant acid ionization or proton transfer was observed in the IL solutions. Raman and IR spectroscopy with computational simulations suggest that the HTFSI forms dimers in the solutions with an N-H-N “bridged” structure, while MSA does not perturb this hydrogen ion solvation structure in the IL solutions. CSA has a lower solubility in the ILs and reduced the IL solution conductivity. However, in IL solutions containing 0.4 M or higher concentration of HTFSI, CSA addition increased the conductivity at low CSA concentrations and reduced it at high concentrations, which may indicate a synergistic effect.

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Characterization of the Bridged Proton Structure in HTFSI Acid Ionic Liquid Solutions

Cited by 17 publications

References 47 publications

A Hydronium Solvate Ionic Liquid: Facile Synthesis of Air-Stable Ionic Liquid with Strong Brønsted Acidity

A Hydronium Solvate Ionic Liquid: Facile Synthesis of Air-Stable Ionic Liquid with Strong Brønsted Acidity

Organic electrochemical transistors based on PEDOT with different anionic polyelectrolyte dopants

Conductivity, Viscosity, Spectroscopic Properties of Organic Sulfonic Acid solutions in Ionic Liquids

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