Hsiu-Wei Cheng

The Effect of Water and Confinement on Self-Assembly of Imidazolium Based Ionic Liquids at Mica Interfaces

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.

In situ nano- to microscopic imaging and growth mechanism of electrochemical dissolution (e.g., corrosion) of a confined metal surface

Significance A surface forces apparatus was used with an electrochemical attachment to directly visualize electrochemical reactions, dissolution, and pitting on surfaces when confined in nanoscale gaps (or “crevices”) in real time. The results provide unique insights into how two closely apposed surfaces degrade under confinement, which is different from degradation of surfaces exposed to bulk solution. Degradation proceeds via local nucleation of “pits” at the periphery or center of the “contact area” that rapidly grow outward (in radius) and, more slowly, in depth, until the pits converge and the whole area has become one large pit. The results on a metal–inorganic interface are similar to previous observations on inorganic interfaces, and support a general mechanism of “pitting corrosion” at confined interfaces. Reactivity in confinement is central to a wide range of applications and systems, yet it is notoriously difficult to probe reactions in confined spaces in real time. Using a modified electrochemical surface forces apparatus (EC-SFA) on confined metallic surfaces, we observe in situ nano- to microscale dissolution and pit formation (qualitatively similar to previous observation on nonmetallic surfaces, e.g., silica) in well-defined geometries in environments relevant to corrosion processes. We follow “crevice corrosion” processes in real time in different pH-neutral NaCl solutions and applied surface potentials of nickel (vs. Ag|AgCl electrode in solution) for the mica–nickel confined interface of total area ∼0.03 mm2. The initial corrosion proceeds as self-catalyzed pitting, visualized by the sudden appearance of circular pits with uniform diameters of 6–7 μm and depth ∼2–3 nm. At concentrations above 10 mM NaCl, pitting is initiated at the outer rim of the confined zone, while below 10 mM NaCl, pitting is initiated inside the confined zone. We compare statistical analysis of growth kinetics and shape evolution of individual nanoscale deep pits with estimates from macroscopic experiments to study initial pit growth and propagation. Our data and experimental techniques reveal a mechanism that suggests initial corrosion results in formation of an aggressive interfacial electrolyte that rapidly accelerates pitting, similar to crack initiation and propagation within the confined area. These results support a general mechanism for nanoscale material degradation and dissolution (e.g., crevice corrosion) of polycrystalline nonnoble metals, alloys, and inorganic materials within confined interfaces.

Lithium-ion battery electrolyte mobility at nano-confined graphene interfaces.

Interfaces are essential in electrochemical processes, providing a critical nanoscopic design feature for composite electrodes used in Li-ion batteries. Understanding the structure, wetting and mobility at nano-confined interfaces is important for improving the efficiency and lifetime of electrochemical devices. Here we use a Surface Forces Apparatus to quantify the initial wetting of nanometre-confined graphene, gold and mica surfaces by Li-ion battery electrolytes. Our results indicate preferential wetting of confined graphene in comparison with gold or mica surfaces because of specific interactions of the electrolyte with the graphene surface. In addition, wetting of a confined pore proceeds via a profoundly different mechanism compared with wetting of a macroscopic surface. We further reveal the existence of molecularly layered structures of the confined electrolyte. Nanoscopic confinement of less than 4–5 nm and the presence of water decrease the mobility of the electrolyte. These results suggest a lower limit for the pore diameter in nanostructured electrodes.

Effect of Concentration on the Interfacial and Bulk Structure of Ionic Liquids in Aqueous Solution

Bio and aqueous applications of ionic liquids (IL) such as catalysis in micelles formed in aqueous IL solutions or extraction of chemicals from biologic materials rely on surface-active and self-assembly properties of ILs. Here, we discuss qualitative relations of the interfacial and bulk structuring of a water-soluble surface-active IL ([C8MIm][Cl]) on chemically controlled surfaces over a wide range of water concentrations using both force probe and X-ray scattering experiments. Our data indicate that IL structuring evolves from surfactant-like surface adsorption at low IL concentrations, to micellar bulk structure adsorption above the critical micelle concentration, to planar bilayer formation in ILs with <1 wt % of water and at high charging of the surface. Interfacial structuring is controlled by mesoscopic bulk structuring at high water concentrations. Surface chemistry and surface charges decisively steer interfacial ordering of ions if the water concentration is low and/or the surface charge is high. We also demonstrate that controlling the interfacial forces by using self-assembled monolayer chemistry allows tuning of interfacial structures. Both the ratio of the head group size to the hydrophobic tail volume as well as the surface charging trigger the bulk structure and offer a tool for predicting interfacial structures. Based on the applied techniques and analyses, a qualitative prediction of molecular layering of ILs in aqueous systems is possible.

Interfacial Layering and Screening Behavior of Glyme-Based Lithium Electrolytes

Understanding of electrical double layers is essential to all electrochemical devices, particularly at high charge carrier concentrations. Using a combined approach (surface force apparatus, zeta potential, infrared spectroscopy), we propose a model for the interfacial structure of triglyme electrolytes on muscovite mica. In contact with the pure triglyme, a brush-like polymeric structure grows on the mica surface. When lithium triflate is present in the triglyme, this structure is suppressed by anion adsorption and an extended double layer is formed. A surprising result of great fundamental significance is that the effective screening length measured by surface force apparatus at considerable lithium triflate concentrations (above 0.2 M) is substantially higher than expected from the Debye-Hückel theory. This suggests a high degree of complex salt association as a novel characteristic feature of salt-containing electrolytes.

Anion Layering and Steric Hydration Repulsion on Positively Charged Surfaces in Aqueous Electrolytes

The molecular structure at charged solid/liquid interfaces is vital for many chemical or electrochemical processes, such as adhesion, catalysis, or the stability of colloidal dispersions. How cations influence structural hydration forces and interactions across negatively charged surfaces has been studied in great detail. However, how anions influence structural hydration forces on positively charged surfaces is much less understood. Herein we report force versus distance profiles on freshly cleaved mica using atomic force microscopy with silicon tips. We characterize steric anion hydration forces for a set of common anions (Cl- , ClO4- , NO3- , SO42- and PO43- ) in pure acids at pH ≈1, where protons are the co-ions. Solutions containing anions with low hydration energies exhibit repulsive structural hydration forces, indicating significant ion and/or water structuring within the first 1-2 nm on a positively charged surface. We attribute this to specific adsorption effects within the Stern layer. In contrast, ions with high hydration energies show exponentially repulsive hydration forces, indicating a lower degree of structuring within the Stern layer. The presented data demonstrates that anion hydration forces in the inner double layer are comparable to cation hydration forces, and that they qualitatively correlate with hydration free energies. This work contributes to understanding interaction processes in which positive charge is screened by anions within an electrolyte.

Interaction Forces between Pegylated Star-Shaped Polymers at Mica Surfaces

We present a study focused on characterizing the interaction forces between mica surfaces across solutions containing star-shaped polymers with cationic ends. Using the surface forces apparatus, we show that the interaction forces in pure water between surfaces covered with the polymers can be adequately described by the dendronized brush model. In that framework, our experimental data suggest that the number of branches adsorbed at the surface decreases as the concentration of polymer in the adsorbing solution increases. The onset of interaction was also shown to increase with the concentration of polymer in solution up to distances much larger than the contour length of the polymer, suggesting that the nanostructure of the polymer film is significantly different from that of a monolayer. High compression of the polymer film adsorbed at low polymer concentration revealed the appearance of a highly structured hydration layer underneath the polymer layer. These results support that charged polymer chains do not necessarily come into close contact with the surface even if strong electrostatic interaction is present. Altogether, our results provide a comprehensive understanding of the interfacial behavior of star-shaped polymers and reveal the unexpected role of hydration water in the control of the polymer conformation.