The confinement of liquids in nanometer-scale gaps can lead to changes in their viscous shear properties. For liquids of polar molecules, the charge state of the confining surfaces has a significant influence on the structure in the confined liquid. Here we report on the implementation of dynamic shear force microscopy in an electrochemical cell. Lateral oscillations of the tip of an atomic force microscope were magnetically activated at a frequency of about 50 kHz. The damping of the lateral tip oscillation was recorded as a function of the tip-sample distance and of the electrode potential at the surface of a Au(100) single crystal electrode. The influence of surface charges on the shear response of the nano-confined liquids was demonstrated for the ionic liquid [EMIM][NTf] and for aqueous NaSO solution.
Molecular mechanisms in the shear of an ionic liquid in nanometer-scale confinement were investigated by atomic force microscopy with a laterally oscillating tip. On a single-crystal gold electrode, the ionic liquid 1-ethyl-3methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM][NTf 2 ]) exhibits molecular ordering in a simple cubic structure upon confinement by the nanometer-sized asperity. The strength of shear resistance decreases exponentially with increasing number of confined molecular layers. The dependence of lateral forces and of dissipation on the applied electrochemical potential confirms a mechanism in the electrolubrication by ionic liquids, namely, the change of the slippage plane from the interface with the electrode into the ionic liquid for increasing surface potential.
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