Phase behaviour and structure of a superionic liquid in nonpolarized nanoconfinement

The ion-ion interactions become exponentially screened for ions confined in ultranarrow metallic pores. To study the phase behaviour of an assembly of such ions, called a superionic liquid, we develop a statistical theory formulated on bipartite lattices, which allows an analytical solution within the Bethe-lattice approach. Our solution predicts the existence of ordered and disordered phases in which ions form a crystal-like structure and a homogeneous mixture, respectively. The transition between these two phases can potentially be first or second order, depending on the ion diameter, degree of confinement and pore ionophobicity. We supplement our analytical results by three-dimensional off-lattice Monte Carlo simulations of an ionic liquid in slit nanopores. The simulations predict formation of ionic clusters and ordered snake-like patterns, leading to characteristic close-standing peaks in the cation-cation and anion-anion radial distribution functions

Crowding-Regulated Binding of Divalent Biomolecules

Macromolecular crowding affects biophysical processes as diverse as diffusion, gene expression, cell growth, and senescence. Yet, there is no comprehensive understanding of how crowding affects reactions, particularly multivalent binding. Herein, we use scaled particle theory and develop a molecular simulation method to investigate the binding of monovalent to divalent biomolecules. We find that crowding can increase or reduce cooperativity--the extent to which the binding of a second molecule is enhanced after binding a first molecule--by orders of magnitude, depending on the sizes of the involved molecular complexes. Cooperativity generally increases when a divalent molecule swells and then shrinks upon binding two ligands. Our calculations also reveal that, in some cases, crowding enables binding that does not occur otherwise. As an immunological example, we consider Immunoglobulin G-antigen binding and show that crowding enhances its cooperativity in bulk but reduces it when an Immunoglobulin G binds antigens on a surface

Probing interface localization-delocalization transitions by colloids

Interface localization-delocalization transitions (ILDT) occur in two-phase fluids confined in a slit with competing preferences of the walls for the two fluid phases. At low temperatures the interface between the two phases is localized at one of the walls. Upon increasing temperature it unbinds. Although intensively studied theoretically and computationally, such transitions have not yet been observed experimentally due to severe challenges in resolving fine details of the fluid structure. Here, using mean field theory and Monte Carlo simulations of the Ising model, we propose to detect these ILDT by using colloids. We show that the finite-size and fluctuation induced force acting on a colloid confined in such a system experiences a vivid change if, upon lowering the temperature, the interface localizes at one of the walls. This change can serve as a more easily accessible experimental indicator of the transition

Optimising nanoporous supercapacitors for heat-to-electricity conversion

Innovative ways of harnessing sustainable energy are needed to meet the world's ever-increasing energy demands. Supercapacitors may contribute, as they can convert waste heat to electricity through cyclic charging and discharging at different temperatures. Herein, we use an analytically-solvable model of a cylindrical pore filled with a single file of ions to identify optimal conditions for heat-to-electricity conversion with supercapacitors. We consider Stirling and Ericsson-like charging cycles and show that the former or latter yields more work when a supercapacitor operates under charge or voltage limitations, respectively. Both cycles yield the most work for pores almost as narrow as the size of the ions they contain, as is the case for energy storage with supercapacitors. In contrast to energy storage, which can be maximised by ionophobic pores, such pores do not yield the best heat-to-electricity conversion, independently of the applied potential. Instead, we find that for a given pore size, a moderately ionophilic pore harvests more work than ionophobic and strongly ionophilic pores

Capacitance-Power-Hysteresis Trilemma in Nanoporous Supercapacitors

Nanoporous supercapacitors are an important player in the field of energy storage that fill the gap between dielectric capacitors and batteries. The key challenge in the development of supercapacitors is the perceived trade-off between capacitance and power delivery. Current efforts to boost the capacitance of nanoporous supercapacitors focus on reducing the pore size so that they can only accommodate a single layer of ions. However, this tight packing compromises the charging dynamics and hence power density. We show via an analytical theory and Monte Carlo simulations that charging is sensitively dependent on the affinity of ions to the pores, and that high capacitances can be obtained for ionophobic pores of widths significantly larger than the ion diameter. Our theory also predicts that charging can be hysteretic with a significant energy loss per cycle for intermediate ionophilicities. We use these observations to explore the parameter regimes in which a capacitance-power-hysteresis trilemma may be avoided

Bridging transitions and capillary forces for colloids in a slit

Capillary bridges can form between colloids immersed in a two phase fluid, e.g., in a binary liquid mixture, if the surface of the colloids prefers the species other than the one favored in the bulk liquid. Here, we study the formation of liquid bridges induced by confining colloids to a slit, with the slit walls having a preference opposite to the one of the colloid surface. Using mean field theory, we show that there is a line of first-order phase transitions between the bridge and the no-bridge states, which ends at a critical point. By decreasing the slit width, this critical point is shifted towards smaller separations between the colloids. However, at very small separations, and far from criticality, we observe only a minor influence of the slit width on the location of the transition. Monte Carlo simulations of the Ising model, which mimics incompressible binary liquid mixtures, confirm the occurrence of the bridging transitions, as manifested by the appearance of bistable regions where both the bridge and the no-bridge configurations are (meta)stable. Interestingly, we find no bistability in the case of small colloids, but we observe a sharpening of the transition when the colloid size increases. In addition, we demonstrate that the capillary force acting between the colloids can depend sensitively on the slit width, and varies drastically with temperature, thus achieving strengths orders of magnitude higher than at criticality of the fluid

Effect of cation size of binary cation ionic liquid mixtures on capacitive energy storage

Ionic liquid mixtures show promise as electrolytes for supercapacitors with nanoporous electrodes. Herein, we investigate theoretically and with experiments how binary electrolytes comprising a common anion and two types of differently-sized cations affect capacitive energy storage. We find that such electrolytes can enhance the capacitance of single nanopores and nanoporous electrodes under potential differences negative relative to the potential of zero charge. For a two-electrode cell, however, they are beneficial only at low and intermediate cell voltages, while a neat ionic liquid performs better at higher voltages. We reveal subtle effects of how the distribution of pores accessible to different types of ions correlates with charge storage and suggest approaches to increase capacitance and stored energy density with ionic liquid mixtures

Dynamics of Ion Transport in Ionic Liquids.

A gap in understanding the link between continuum theories of ion transport in ionic liquids and the underlying microscopic dynamics has hindered the development of frameworks for transport phenomena in these concentrated electrolytes. Here, we construct a continuum theory for ion transport in ionic liquids by coarse graining a simple exclusion process of interacting particles on a lattice. The resulting dynamical equations can be written as a gradient flow with a mobility matrix that vanishes at high densities. This form of the mobility matrix gives rise to a charging behavior that is different to the one known for electrolytic solutions, but which agrees qualitatively with the phenomenology observed in experiments and simulations