Electric double layers

1. Effect of Interfacial Ion Structuring on Range and Magnitude of Electric Double Layer, Hydration, and Adhesive Interactions between Mica Surfaces in 0.05–3 M Li+ and Cs+ Electrolyte Solutions

Ions and water structuring at charged–solid/electrolyte interfaces and forces arising from interfacial structuring in solutions above 100 mM concentrations dominate structure and functionality in many physiological, geological, and technological systems. In these concentrations, electrolyte structuring occurs within the range of molecular dimensions. Here, we quantitatively measure and describe electric double layer (EDL) and adhesive interactions at mica–interfaces in aqueous CsCl and LiCl solutions with concentrations ranging from 50 mM to 3 M. Complementarily, using atomic force microscopy and surface forces apparatus experiments we characterize concentration-dependent stark differences in the inner and outer EDL force profiles, and discuss differences between the used methods. From 50 mM to 1 M concentrations, interactions forces measured in CsCl-solutions exhibit strong hydration repulsions, but no diffuse EDL-repulsions beyond the Stern layer. In confinement the weakly hydrated Cs+ ions condensate into the mica-lattice screening the entire surface charge within the Stern layer. In contrast, strongly hydrated Li+ ions only partially compensate the surface charge within the Stern layer, leading to the formation of a diffuse outer double layer with DLVO behavior. Both LiCl and CsCl solutions exhibit oscillatory ion-hydration forces at surface separations from 2.2 nm to 4–8 Å. Below 4–8 Å the force profiles are dominated in both cases by forces originating from water and/or ion confinement at the solid/electrolyte/solid interface. Adhesive minima and their location vary strongly with the electrolyte and its concentration due to specific ion correlations across the interface, while dispersion forces between the surfaces are overpowered. Highly concentrated 3 M solutions exhibit solidification of the inner EDL structure and an unexpected formation of additional diffuse EDL forces with an increasing range, as recently measured in ionic liquids. Our results may have important implications for understanding and modeling of interaction forces present in static and dynamic systems under physiological and high salt conditions.

Theodoros Baimpos, Buddha Ratna Shrestha, Sangeetha Raman, and Markus Valtiner, "Effect of interfacial ion structuring on range and magnitude of electric double layer, hydration, and adhesive interactions between mica surfaces in 0.05-3 M Li+ and Cs+ electrolyte solutions," Langmuir 30, 4322-4332 (2014).

2. Effect of Surface Roughness and Electrostatic Surface Potentials on Forces Between Dissimilar Surfaces in Aqueous Solution

The first surface force measurements under electrochemical potential control between a metal and a ceramic surface across a liquid medium (water) are reported. Our experiments also investigate and reveal how increasing levels of surface roughness and dissimilarity between the potentials of the interacting surfaces influence the strength and range of electric double layer, van der Waals, hydration, and steric forces and how this contributes to deviations from DLVO theory at small distances within aqueous solution.

Markus Valtiner, Kai Kristiansen, George Wren Greene, and Jacob N. Israelachvili, "Effect of surface roughness and electrostatic surface potentials on forces between dissimilar surfaces in aqueous solution," Advanced Materials 23 (20), 2294-2299 (2011).

3. The Electrochemical Surface Forces Apparatus: The Effect of Surface Roughness, Electrostatic Surface Potentials, and Anodic Oxide Growth on Interaction Forces, and Friction between Dissimilar Surfaces in Aqueous Solutions

We present a newly designed electrochemical surface forces apparatus (EC-SFA) that allows control and measurement of surface potentials and interfacial electrochemical reactions with simultaneous measurement of normal interaction forces (with nN resolution), friction forces (with μN resolution), and distances (with Å resolution) between apposing surfaces. We describe three applications of the developed EC-SFA and discuss the wide-range of potential other applications. In particular, we describe measurements of (1) force–distance profiles between smooth and rough gold surfaces and apposing self-assembled monolayer-covered smooth mica surfaces; (2) the effective changing thickness of anodically growing oxide layers with Å-accuracy on rough and smooth surfaces; and (3) friction forces evolving at a metal–ceramic contact, all as a function of the applied electrochemical potential. Interaction forces between atomically smooth surfaces are well-described using DLVO theory and the Hogg–Healy–Fuerstenau approximation for electric double layer interactions between dissimilar surfaces, which unintuitively predicts the possibility of attractive double layer forces between dissimilar surfaces whose surface potentials have similar sign, and repulsive forces between surfaces whose surface potentials have opposite sign. Surface roughness of the gold electrodes leads to an additional exponentially repulsive force in the force–distance profiles that is qualitatively well described by an extended DLVO model that includes repulsive hydration and steric forces. Comparing the measured thickness of the anodic gold oxide layer and the charge consumed for generating this layer allowed the identification of its chemical structure as a hydrated Au(OH)3 phase formed at the gold surface at high positive potentials. The EC-SFA allows, for the first time, one to look at complex long-term transient effects of dynamic processes (e.g., relaxation times), which are also reflected in friction forces while tuning electrochemical surface potentials.

M. Valtiner, X. Banquy, K. Kristiansen, G. W. Greene, and J. N. Israelachvili, "The Electrochemical Surface Forces Apparatus: The Effect of Surface Roughness, Electrostatic Surface Potentials, and Anodic Oxide Growth on Interaction Forces, and Friction between Dissimilar Surfaces in Aqueous Solutions," Langmuir 28 (36), 13080-13093 (2012).

4. Real-Time view into reactively changing electric double layers

Electrochemical solid|liquid interfaces are critically important for technological applications and materials for energy storage, harvesting, and conversion. Yet, a real-time Angstrom-resolved visualization of dynamic processes at electrified solid|liquid interfaces has not been feasible. We recently revealed hitherto unknown strong electrochemical reaction forces, which are due to temporary charge imbalance in the electric double layer caused by depletion/generation of charged species. The real-time capability of our novel approach reveals significant time lags between electron transfer, oxide reduction/oxidation, and solution side reaction during a progressing electrode process. Comparing the kinetics of solution and metal side responses provides evidence that noble metal oxide reduction proceeds via a hydrogen adsorption and subsequent dissolution/redeposition mechanism. Our findings may have important implications for designing emerging materials utilizing electrified interfaces and may apply to bioelectrochemical processes and signal transmission.

Buddha R. Shrestha, Theodoros Baimpos, Sangeetha Raman, and Markus Valtiner, "Angstrom-resolved real-time dissection of electrochemically active noble metal interfaces," ACS Nano 8 (6), 5979-5987 (2014).
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