title: The Effect of Water and Confinement on Self-Assembly of Imidazolium Based Ionic Liquids at Mica Interfaces.
abstract: Tuning chemical structure and molecular layering of ionic liquids (IL) at solid interfaces offers leverage to tailor performance of ILs in applications such as super-capacitors, catalysis or lubrication. Recent experimental interpretations suggest that ILs containing cations with long hydrophobic tails form well-ordered bilayers at interfaces. Here we demonstrate that interfacial bilayer formation is not an intrinsic quality of hydrophobic ILs. In contrast, bilayer formation is triggered by boundary conditions including confinement, surface charging and humidity present in the IL. Therefore, we performed force versus distance profiles using atomic force microscopy and the surface forces apparatus. Our results support models of disperse low-density bilayer formation in confined situations, at high surface charging and/or in the presence of water. Conversely, interfacial structuring of long-chain ILs in dry environments and at low surface charging is disordered and dominated by bulk structuring. Our results demonstrate that boundary conditions such as charging, confinement and doping by impurities have decisive influence on structure formation of ILs at interfaces. As such, these results have important implications for understanding the behavior of solid/IL interfaces as they significantly extend previous interpretations.
authors.affiliation: Department for Interface Chemistry and Surface Engineering, Max-Planck-Institute f. Eisenforschung GmbH, D-40213 Düsseldorf, Germany.|Department for Interface Chemistry and Surface Engineering, Max-Planck-Institute f. Eisenforschung GmbH, D-40213 Düsseldorf, Germany.
authors.forename: H-W
authors.initials: HW
authors.lastname: Cheng
authors.affiliation: Department for Interface Chemistry and Surface Engineering, Max-Planck-Institute f. Eisenforschung GmbH, D-40213 Düsseldorf, Germany.|Department for Interface Chemistry and Surface Engineering, Max-Planck-Institute f. Eisenforschung GmbH, D-40213 Düsseldorf, Germany.
authors.forename: J-N
authors.initials: JN
authors.lastname: Dienemann
authors.affiliation: Department for Interface Chemistry and Surface Engineering, Max-Planck-Institute f. Eisenforschung GmbH, D-40213 Düsseldorf, Germany.|Department for Interface Chemistry and Surface Engineering, Max-Planck-Institute f. Eisenforschung GmbH, D-40213 Düsseldorf, Germany.
authors.forename: P
authors.initials: P
authors.lastname: Stock
authors.affiliation: Department for Interface Chemistry and Surface Engineering, Max-Planck-Institute f. Eisenforschung GmbH, D-40213 Düsseldorf, Germany.|Department for Interface Chemistry and Surface Engineering, Max-Planck-Institute f. Eisenforschung GmbH, D-40213 Düsseldorf, Germany.
authors.forename: C
authors.initials: C
authors.lastname: Merola
authors.affiliation: Department for Interface Chemistry and Surface Engineering, Max-Planck-Institute f. Eisenforschung GmbH, D-40213 Düsseldorf, Germany.|Department for Interface Chemistry and Surface Engineering, Max-Planck-Institute f. Eisenforschung GmbH, D-40213 Düsseldorf, Germany.
authors.forename: Y-J
authors.initials: YJ
authors.lastname: Chen
authors.affiliation: Department for Interface Chemistry and Surface Engineering, Max-Planck-Institute f. Eisenforschung GmbH, D-40213 Düsseldorf, Germany.|Technische Universität Bergakademie Freiberg, Physikalische Chemie II, D-09599 Freiberg, Germany.
authors.forename: M
authors.initials: M
authors.lastname: Valtiner