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    Force microscopy of layering and friction in an ionic liquid
    (Bristol : IOP Publishing, 2014) Hoth, Judith; Hausen, Florian; Müser, Martin H.; Bennewitz, Roland
    The mechanical properties of the ionic liquid 1-butyl-1-methylpyrrolidinium tris(pentafluoroethyl) trifluorophosphate ([Py1,4][FAP]) in confinement between a SiOx and a Au(1 1 1) surface are investigated by means of atomic force microscopy (AFM) under electrochemical control. Up to 12 layers of ion pairs can be detected through force measurements while approaching the tip of the AFM to the surface. The particular shape of the force versus distance curve is explained by a model for the interaction between tip, gold surface and ionic liquid, which assumes an exponentially decaying oscillatory force originating from bulk liquid density correlations. Jumps in the tip–sample distance upon approach correspond to jumps of the compliant force sensor between branches of the oscillatory force curve. Frictional force between the laterally moving tip and the surface is detected only after partial penetration of the last double layer between tip and surface.
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    Friction mediated by redox-active supramolecular connector molecules
    (Washington D.C. : American Chemical Society, 2015) Bozna, Bianca L.; Blass, Johanna; Albrecht, Marcel; Hausen, Florian; Wenz, Gerhard; Bennewitz, Roland
    We report on a friction study at the nanometer scale using atomic force microscopy under electrochemical control. Friction arises from the interaction between two surfaces functionalized with cyclodextrin molecules. The interaction is mediated by connector molecules with (ferrocenylmethyl)ammonium end groups forming supramolecular complexes with the cyclodextrin molecules. With ferrocene connector molecules in solution, the friction increases by a factor of up to 12 compared to control experiments without connector molecules. The electrochemical oxidation of ferrocene to ferrocenium causes a decrease in friction owing to the lower stability of ferrocenium−cyclodextrin complex. Upon switching between oxidative and reduction potentials, a change in friction by a factor of 1.2−1.8 is observed. Isothermal titration calorimetry reveals fast dissociation and rebinding kinetics and thus an equilibrium regime for the friction experiments.
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    Relaxation Times of Ionic Liquids under Electrochemical Conditions Probed by Friction Force Microscopy
    (Weinheim : WILEY-VCH Verlag GmbH & Co. KGaA, 2023) Hausen, Florian
    Ionic liquids (ILs) represent an important class of liquids considered for a broad range of applications such as lubrication, catalysis, or as electrolytes in batteries. It is well-known that in the case of charged surfaces, ILs form a pronounced layer structure that can be easily triggered by an externally applied electrode potential. Information about the time required to form a stable interface under varying electrode potentials is of utmost importance in many applications. For the first time, probing of relaxation times of ILs by friction force microscopy is demonstrated. The friction force is extremely sensitive to even subtle changes in the interfacial configuration of ILs. Various relaxation processes with different time scales are observed. A significant difference dependent on the direction of switching the applied potential, i.e., from a more cation-rich to a more anion-rich interface or vice versa, is found. Furthermore, variations in height immediately after the potential step and the presence of trace amounts of water are discussed as well.