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Cation Exchange at the Interfaces of Ultrathin Films of Fluorous Ionic Liquids on Ag(111).

ABSTRACT: In the context of applications with thin ionic liquid (IL) films on solid supports, we studied the ion distribution within mixed thin IL films by angle-resolved X-ray photoelectron spectroscopy. After the deposition of 1-methyl-3-octylimidazolium hexafluorophosphate, [C₈C₁Im][PF₆], on top of a wetting layer (WL) of 3-methyl-1-(3,3,4,4,4-pentafluorobutyl)imidazolium hexafluorophosphate, [PFBMIm][PF₆], on Ag(111) at room temperature (RT), we find a preferential enrichment of the [PFBMIm]⁺ cation at the IL/vacuum interface. In a similar deposition experiment at 82 K, this cation exchange at the IL/solid interface does not occur. Upon heating the film from 82 K to RT, we observe the replacement of [C₈C₁Im]⁺ by [PFBMIm]⁺ at the IL/vacuum interface between ?160 and ?220 K. No further changes in the surface composition were observed between 220 K and RT. Upon further heating the mixed IL film, we find the complete desorption of [PFBMIm][PF₆] from the mixed film below 410 K, leaving a WL of pure [C₈C₁Im][PF₆] on Ag(111), which desorbs until 455 K.

SUBMITTER: Lexow M

PROVIDER: S-EPMC6377181 | biostudies-literature | 2019 Jan

REPOSITORIES: biostudies-literature

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Cation Exchange at the Interfaces of Ultrathin Films of Fluorous Ionic Liquids on Ag(111).

Lexow Matthias M Heller Bettina S J BSJ Partl Gabriel G Bhuin Radha G RG Maier Florian F Steinrück Hans-Peter HP

Langmuir : the ACS journal of surfaces and colloids 20181227 2

In the context of applications with thin ionic liquid (IL) films on solid supports, we studied the ion distribution within mixed thin IL films by angle-resolved X-ray photoelectron spectroscopy. After the deposition of 1-methyl-3-octylimidazolium hexafluorophosphate, [C8C1Im][PF6], on top of a wetting layer (WL) of 3-methyl-1-(3,3,4,4,4-pentafluorobutyl)imidazolium hexafluorophosphate, [PFBMIm][PF6], on Ag(111) at room temperature (RT), we find a prefe ...[more]

PMID: 30540199

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Project description:We evaluate the influence of Li-salt doping on the dynamics, capacitance, and structure of three ionic liquid electrolytes, [pyr14][TFSI], [pyr13][FSI], and [EMIM][BF4], using molecular dynamics and polarizable force fields. In this respect, our focus is on the properties of the electric double layer (EDL) formed by the electrolytes at the electrode surface as a function of surface potential (Ψ). The rates of EDL formation are found to be on the order of hundreds of picoseconds and only slightly influenced by the addition of Li-salt. The EDLs of three electrolytes are shown to have different energy storage capacities, which we relate to the EDL formation free energy. The differential capacitance obtained from our computations exhibits asymmetry about the potential of zero charge and is consistent with the camel-like profiles noted from mean field theories and experiments on metallic electrodes. The introduction of Li-salt reduces the noted asymmetry in the differential capacitance profile. Complementary experimental capacitance measurements have been made on our three electrolytes in their neat forms and with Li-salt. The measurements, performed on glassy carbon electrodes, produce U-like profiles, and Li-salt doping is shown to strongly affect capacitance at high magnitudes of Ψ. Differences in the theoretical and experimental shapes and magnitudes of capacitance are rationalized in terms of the electrode surface and pseudocapacitive effects. In both neat and Li-doped liquids, the details of the computational capacitance profile are well described by Ψ-induced changes in the density and molecular orientation of ions in the molecular layer closest to the electrode. Our results suggest that the addition of Li+ induces disorder in the EDL, which originates from the strong binding of anions to Li+. An in-depth analysis of the distribution of Li+ in the EDL reveals that it does not readily enter the molecular layer at the electrode surface, preferring instead to be localized farther away from the surface in the second molecular layer. This behavior is validated through an analysis of the free energy of Li+ solvation as a function of distance from the electrode. Free energy wells are found to coincide with localized concentrations of Li+, the depths of which increase with Ψ and suggest a source of impedance for Li+ to reach the electrode. Finally, we make predictions of the specific energy at ideal graphite utilizing the computed capacitance and previously derived electrochemical windows of the liquids.

Dataset Information

Cation Exchange at the Interfaces of Ultrathin Films of Fluorous Ionic Liquids on Ag(111).

Publications

Cation Exchange at the Interfaces of Ultrathin Films of Fluorous Ionic Liquids on Ag(111).

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