Interfacial nanostructure and friction of a polymeric ionic liquid-ionic liquid mixture as a function of potential at Au(111) electrode interface

Hypothesis The polymeric cations of polymeric ionic liquids (PILs) can adsorb from the bulk of a conventional ionic liquid (IL) to the Au(1 1 1) electrode interface and form a boundary layer. The interfacial properties of the PIL boundary layer may be tuned by potential. Experiments Atomic force microscopy has been used to investigate the changes of surface morphology, normal and lateral forces of a 5 wt% PIL/IL mixture as a function of potential. Findings Polymeric cations adsorb strongly to Au(1 1 1) and form a polymeric cation-enriched boundary layer at −1.0 V. This boundary layer binds less strongly to the surface at open circuit potential (OCP) and weakly at + 1.0 V. The polymeric cation chains are compressed at −1.0 V and OCP owing to electrical attractions with the electrode surface, but fully stretched at + 1.0 V due to electrical repulsions. The lateral forces of the 5 wt% PIL/IL mixture at −1.0 V and OCP are higher than at + 1.0 V as the polymeric cation-enriched boundary layer is rougher and has stronger interactions with the AFM probe; at + 1.0 V, the lateral force is low and comparable to pure conventional IL due to displacement of polymeric cations with conventional anions in the boundary layer.