We review direct force measurements on a broad class of hydrophobic and hydrophilic surfaces. These measurements have enabled the development of a general interaction potential per unit area, W(D) = -2γ(i)Hy exp(-D/D(H)) in terms of a nondimensional Hydra parameter, Hy, that applies to both hydrophobic and hydrophilic interactions between extended surfaces. This potential allows one to quantitatively account for additional attractions and repulsions not included in the well-known combination of electrostatic double layer and van der Waals theories, the so-called Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. The interaction energy is exponentially decaying with decay length D(H) ≈ 0.3-2 nm for both hydrophobic and hydrophilic interactions, with the exact value of D(H) depending on the precise system and conditions. The pre-exponential factor depends on the interfacial tension, γ(i), of the interacting surfaces and Hy. For Hy > 0, the interaction potential describes interactions between partially hydrophobic surfaces, with the maximum hydrophobic interaction (i.e., two fully hydrophobic surfaces) corresponding to Hy = 1. Hydrophobic interactions between hydrophobic monolayer surfaces measured with the surface forces apparatus (SFA) are shown to be well described by the proposed interaction potential. The potential becomes repulsive for Hy < 0, corresponding to partially hydrophilic (hydrated) interfaces. Hydrated surfaces such as mica, silica, and lipid bilayers are discussed and reviewed in the context of the values of Hy appropriate for each system.

The importance of water on molecular ion structuring and charging mechanism of solid interfaces in room temperature ionic liquid (RTIL) is unclear and has been largely ignored. Water may alter structures, charging characteristics, and hence performance at electrified solid/RTIL interfaces and is utilized in various fields including energy storage, conversion, or catalysis. Here, atomic force microscopy and surface forces apparatus experiments are utilized to directly measure how water alters the interfacial structuring and charging characteristics of [C2mim][Tf2N] on mica and electrified gold surfaces. On hydrophilic and ionophobic mica surfaces, water‐saturated [C2mim][Tf2N] dissolves surface‐bound cations, which leads to high surface charging and strong layering. In contrast, layering of dry RTIL at weakly charged mica surfaces is weakly structured. At electrified, hydrophobic, and ionophilic gold electrodes, significant water effects are found only at positive applied electrochemical potentials. Here, the influence of water is limited to interactions within the RTIL layers, and is not related to a direct electrosorption of water on the polarized electrode. More generally, the results suggest that effects of water on interfacial structuring of RTIL strongly depend on both (1) surface charging mechanism and (2) interfacial wetting properties. This may greatly impact utilization/design of RTILs and surfaces for interface‐dominated processes.

High oxygen evolution reaction activity of ruthenium and long term stability of iridium in acidic electrolytes make their mixed oxides attractive candidates for utilization as anodes in water electrolyzers. Indeed, such materials were addressed in numerous previous studies. The application of a scanning flow cell connected to an inductively coupled plasma mass spectrometer allowed us now to examine the stability and activity toward oxygen evolution reaction of such mixed oxides in parallel. The whole composition range of Ir-Ru mixtures has been covered in a thin film material library. In the whole composition range the rate of Ru dissolution is observed to be much higher than that of Ir. Eventually, due to the loss of Ru, the activity of the mixed oxides approaches the value corresponding to pure IrO 2 . Interestingly, the loss of only a few percent of a monolayer in Ru surface concentration results in a significant drop in activity. Several explanations of this phenomenon are discussed. It is concluded that the herein observed stability of mixed Ir-Ru oxide systems is most likely a result of high corrosion resistance of the iridium component, but not due to an alteration of the material's electronic structure. Renewable primary energies such as solar energy, wind energy and ocean energy receive more and more attention and are increasingly installed around the world.1-3 It is anticipated that renewables will eventually replace traditional fossil fuel-burning and nuclear power plants. However, intermittent power supply of renewables means that energy needs to be buffered. Thereby, hydrogen produced by water electrolysis is considered as an ideal energy carrier to adjust the balance between the generation of power by renewable primary energy and energy demand for end-use.3-5 Currently, acidic proton exchange membrane water electrolysis (PEMWE) is considered as a promising technology for this purpose. However, the widespread use of PEMWE is hindered by high capital costs, low efficiency, and shortages related to performance deterioration with time. 6 In this connection the nature of electrocatalysts and the procedure of their production and application conditions play a critical role. Materials used as electrocatalysts must be as active as possible to improve efficiency, while at the same time they need to be stable to maintain this efficiency throughout the lifetime of the electrolyzer. This is especially critical for materials catalyzing the anodic oxygen evolution reaction (OER), because of the detrimental positive potential and highly corrosive acidic environment. Only a few catalysts are able to withstand these harsh conditions, while providing sufficient activity, conductivity and mechanical stability. In fact, only iridium oxide anodes are proven to provide the required longevity of operation. On the other hand, ruthenium shows the highest electrocatalytic activity toward this reaction. 7,8 During the last decades, the electrochemical and surface properties of anodes based on these metals and their oxides we...

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.