Graphene is a promising next-generation conducting material with the potential to replace traditional electrode materials in supercapacitors. Since energy storage in supercapacitors relies on the electrolyte-electrode interface, here we elucidate the interfacial subnanometer structure of a single component liquid composed solely of cations and anions – an ionic liquid- on electrified graphene. We study the effect of applied potential on the interaction between graphene and a silicon tip in an ionic liquid and describe it within the framework of the Derjaguin-Landau-Verwey-Overbeck (DLVO) theory. The energy is stored in an electrical double layer composed of an extended Stern layer, which consists of multiple ion layers over ~2 nanometers, beyond which a diffuse layer forms to compensate the applied potential on graphene. The electrical double layer significantly responds to the applied potential, and it shows the transition from overscreening to crowding of counterions at the interface at the highest applied potentials. It is proposed that surface charging occurs through the adsorption of the imidazolium cation to unbiased graphene (likely due to π-π interactions) and that the surface potential is better compensated when counterion crowding happens. This study scrutinizes the electrified graphene-ionic liquid interface, with implications not only in the field of energy storage, but also in lubrication.

Repeatedly applied nanoconfinement of [HMIM] EtSO ₄ between mica surfaces induces a long-range liquid-to-solid transition that remains after confinement has been removed.

The friction between two adjacent tectonic plates under shear loading may dictate seismic activities. To advance the understanding of mechanisms underlying fault strength, we investigate the frictional characteristics of calcite in an aqueous environment. By conducting single-asperity friction experiments using an atomic force microscope, here we show three pathways of energy dissipation with increasing contact stresses: viscous shear of a lubricious solution film at low normal stresses; shear-promoted thermally activated slip, similar to dry friction but influenced by the hydrated ions localized at the interface; and pressure-solution facilitated slip at sufficiently high stresses and slow sliding velocities, which leads to a prominent decrease in friction. It is also shown that the composition of the aqueous solution affects the frictional response. We use this nanoscale evidence to scrutinize the role of brines on fault behavior and argue that pressure solution provides a weakening mechanism of the fault strength at the level of single-asperity contacts.

With reference to our previous surface-force study on 1-hexyl-3-methylimidazolium ethylsulfate ([HMIM] EtSO₄) using an extended surface forces apparatus, which showed an ordered structure within the nanoconfined dry ionic liquid (IL) between mica surfaces that extended up to ∼60 nm from the surface, this work focuses on the influence of the environmental humidity on the bulk, interfacial and nanoconfined structure of [HMIM] EtSO₄. Infrared spectroscopy and rheometry reflect the changes in chemical and physical properties of the bulk IL due to the uptake of water when exposed to ambient humidity, while wide-angle X-ray scattering shows a mild swelling of the bulk nanostructure, and the AFM sharp tip reveals an additional surface layer at the mica–IL interface. When the water-containing [HMIM] EtSO₄ is nanoconfined between two mica surfaces, no long-range order is detected, in contrast to the results obtained for the dry IL, which demonstrates that the presence of water can prevent the liquid-to-solid transformation of this IL. A combination of techniques and the calculated Bjerrum length indicate that water molecules weaken interionic electrostatic and hydrogen-bonding interactions, which lessens ion–ion correlations. Our work shows that the solid-like behavior of the nanoconfined IL strongly depends on the presence of absorbed water and hence, it has implications with regard to the correct interpretation of laboratory studies and their extension to real applications in lubrication.

Little is known about the influence of nanoconfinement on calcium carbonate mineralization. Here, colloidal probe atomic force microscopy is used to confine the calcite–solution interface with a silica microsphere and to measure Derjaguin–Landau–Verwey–Overbeek (DLVO) and non-DLVO forces as a function of the calcium concentration, also after charge reversal of both surfaces occurs. Through the statistical analysis of the oscillatory component of a strong hydration force, the subnanometer interfacial structure of the confined atomically flat calcite is resolved in aqueous solution. By applying a mechanical work, both water and hydrated counterions are squeezed out from the nanoconfined solution, leaving the calcite surface more negatively charged than the analogous unconfined surfaces. Layer size and applied work allow a distinction between the hydration states of the counterions in the Stern layer; we propose counterions to be inner- and outer-sphere calcium ions, with a population of inner-sphere calcium ions larger than on unconfined calcite surfaces. It is also shown that the composition of the nanoconfined solution can be tuned by varying calcium concentration. This is a fundamental study of DLVO and hydration forces, and of their connection, on atomically flat calcite. More broadly, our work scrutinizes the greatly unexplored relation between surface science and confined mineralization, with implications for diverse areas of inquiry, such as nanoconfined biomineralization, CO₂ sequestration in porous aquifers, and pressure solution and crystallization in confined hydrosystems. Significance Calcium carbonate mineralization occurring in confined spaces and nanopores is central to many natural processes occurring at or near the Earth’s surface. We study the effect of divalent ion concentration, in an attempt to provide a general conceptual picture of Derjaguin–Landau–Verwey–Overbeek (DLVO) and non-DLVO forces considering calcite’s nonclassical Stern layer. From the careful measurement of the hydration forces in aqueous solutions, we propose a model for the nanoconfined calcite–solution interface. Colloidal probe AFM resolves subnanometer film thickness transitions of the nanoconfined aqueous solution induced by the squeezing out of water and hydrated calcium ions by applying an external work. The fundamental knowledge derived from this work provides guidance to understand the physicochemical phenomena occurring at nanoconfined mineral interfaces.