Switchable modes of azulene-based single molecule-electrode coupling controlled by interfacial charge distribution.

Molecule-electrode interactions are critical for determining transport mechanisms and device functionalities in both single-molecule electrochemistry and electronics. Crucial factors such as anchoring groups and local fields have been studied, but the role of electrolytes and interfacial charge distribution remains largely underexplored. The present research focuses on how the interfacial charge distribution in the electric double layer (EDL) controls single-molecule junctions anchored by azulene.

Nonlocal structural effects of water on DNA homology recognition.

The mechanism behind mutual recognition of homologous DNA sequences prior to genetic recombination is one of the remaining puzzles in molecular biology. Leading models of homology recognition, based on classical electrostatics, neglect the short-range nonlocal screening effects arising from structured water around DNA, and hence may only provide insight for relatively large separations between interacting DNAs. We elucidate the role of the effects of the nonlocal dielectric response of water on DNA-DNA interaction and show that these can dramatically enhance the driving force for recognition.

Organic Solvent Boosts Charge Storage and Charging Dynamics of Conductive MOF Supercapacitors.

Conductive metal-organic frameworks (c-MOFs) and ionic liquids (ILs) have emerged as auspicious combinations for high-performance supercapacitors. However, the nanoconfinement from c-MOFs and high viscosity of ILs slow down the charging process. This hindrance can, however, be resolved by adding solvent.

Electric field of DNA in solution: who is in charge?

In solution, DNA is a highly charged macromolecule which bears a unit of negative charge on each phosphate of its sugar-phosphate backbone. Although partially compensated by counterions adsorbed at or condensed near it, DNA still produces a substantial electric field in its vicinity, which is screened by buffer electrolyte at longer distances from the DNA. Such field has been explored so far predominantly within the scope of a primitive model of the electrolytic solution, not considering more complicated structural effects of the water solvent.

Ionotronics for reverse actuation.

In the midst of an ongoing energy crisis, the search for new methods of energy harvesting has never been more important. Here we explore, analyse and discuss principles of ionotronic reverse-actuator devices based on the effect of double-layer charging. The designs that we consider in this paper operate based on a common principle - using external mechanical work, which would otherwise be wasted, to produce changes in the contact area of electrode and electrolyte, translated into the time variation of the double-layer capacitance.

Orientational Ordering in Nano-confined Polar Liquids.

Water and other polar liquids exhibit nanoscale structuring near charged interfaces. When a polar liquid is confined between two charged surfaces, the interfacial solvent layers begin to overlap, resulting in solvation forces. Here, we perform molecular dynamics simulations of polar liquids with different dielectric constants and molecular shapes and sizes confined between charged surfaces, demonstrating strong orientational ordering in the nanoconfined liquids.

Theory and Simulations of Ionic Liquids in Nanoconfinement.

Room-temperature ionic liquids (RTILs) have exciting properties such as nonvolatility, large electrochemical windows, and remarkable variety, drawing much interest in energy storage, gating, electrocatalysis, tunable lubrication, and other applications. Confined RTILs appear in various situations, for instance, in pores of nanostructured electrodes of supercapacitors and batteries, as such electrodes increase the contact area with RTILs and enhance the total capacitance and stored energy, between crossed cylinders in surface force balance experiments, between a tip and a sample in atomic force microscopy, and between sliding surfaces in tribology experiments, where RTILs act as lubricants. The properties and functioning of RTILs in confinement, especially nanoconfinement, result in fascinating structural and dynamic phenomena, including layering, overscreening and crowding, nanoscale capillary freezing, quantized and electrotunable friction, and superionic state.

Energy Storage Mechanism in Supercapacitors with Porous Graphdiynes: Effects of Pore Topology and Electrode Metallicity.

Porous graphdiynes are a new class of porous 2D materials with tunable electronic structures and various pore structures. They have potential applications as well-defined nanostructured electrodes and can provide platforms for understanding energy storage mechanisms underlying supercapacitors. Herein, the effect of stacking structure and metallicity on energy storage with such electrodes is investigated.

Electrochemical photonics: a pathway towards electrovariable optical metamaterials.

This review article focuses on the latest achievements in the creation of a class of electrotuneable optical metamaterials for switchable mirrors/windows, variable colour mirrors, optical filters, and SERS sensors, based on the voltage-controlled self-assembly of plasmonic nanoparticles at liquid/liquid or solid/liquid electrochemical interfaces. Practically, these experimental systems were navigated by physical theory, the role of which was pivotal in defining the optimal conditions for their operation, but which itself was advanced in feedback with experiments. Progress and problems in the realisation of the demonstrated effects for building the corresponding devices are discussed.

Less Is More: Can Low Quantum Capacitance Boost Capacitive Energy Storage?

We present a theoretical analysis of charge storage in electrochemical capacitors with electrodes based on carbon nanotubes. Using exact analytical solutions supported by Monte Carlo simulations, we show how the limitations of the electron density of states in such low-dimensional electrode materials may help boost the energy stored at increased voltages. While these counterintuitive predictions await experimental verification, they suggest exciting opportunities for enhancing energy storage by rational engineering of the electronic properties of low-dimensional electrodes.

Electrochemically controlled rectification in symmetric single-molecule junctions.

Single-molecule electrochemical science has advanced over the past decades and now extends well beyond molecular imaging, to molecular electronics functions such as rectification and amplification. Rectification is conceptually the simplest but has involved mostly challenging chemical synthesis of asymmetric molecular structures or asymmetric materials and geometry of the two enclosing electrodes. Here we propose an experimental and theoretical strategy for building and tuning in situ (in operando) rectification in two symmetric molecular structures in electrochemical environment.

Gelation, clustering, and crowding in the electrical double layer of ionic liquids.

Understanding the bulk and interfacial properties of super-concentrated electrolytes, such as ionic liquids (ILs), has attracted significant attention lately for their promising applications in supercapacitors and batteries. Recently, McEldrew et al. [J.

Optical response of hyperbolic metamaterials with adsorbed nanoparticle arrays.

Experimental studies of have been recently performed to determine the optical effect of adsorption of arrays of gold nanoparticles, NPs (16 nm or 40 nm in diameter) on reflective substrates (Ma , , 2018, , 4604-4616; Ma , , 2020, , 328-336) and on transparent interfaces (Montelongo , , 2017, 16, 1127-1135). As predicted by the theory (Sikdar , , 2016, , 20486-20498), a reflection quenching effect was observed on the reflective substrates, in the frequency domain centred around the nanoparticle localised plasmon resonance. Those results showed a broad dip in reflectivity, which was deepening and red-shifting with increasing array densities.

Polar liquids at charged interfaces: A dipolar shell theory.

The structure of polar liquids and electrolytic solutions, such as water and aqueous electrolytes, at interfaces underlies numerous phenomena in physics, chemistry, biology, and engineering. In this work, we develop a continuum theory that captures the essential features of dielectric screening by polar liquids at charged interfaces, including decaying spatial oscillations in charge and mass, starting from the molecular properties of the solvent. The theory predicts an anisotropic dielectric tensor of interfacial polar liquids previously studied in molecular dynamics simulations.

Electrotunable friction with ionic liquid lubricants.

Room-temperature ionic liquids and their mixtures with organic solvents as lubricants open a route to control lubricity at the nanoscale via electrical polarization of the sliding surfaces. Electronanotribology is an emerging field that has a potential to realize in situ control of friction-that is, turning the friction on and off on demand. However, fulfilling its promise needs more research.

Ionic liquids in conducting nanoslits: how important is the range of the screened electrostatic interactions?

Analytical models for capacitive energy storage in nanopores attract growing interest as they can provide in-depth analytical insights into charging mechanisms. So far, such approaches have been limited to models with nearest-neighbor interactions. This assumption is seemingly justified due to a strong screening of inter-ionic interactions in narrow conducting pores.

Conductive Metal-Organic Frameworks for Supercapacitors.

As a class of porous materials with crystal lattices, metal-organic frameworks (MOFs), featuring outstanding specific surface area, tunable functionality, and versatile structures, have attracted huge attention in the past two decades. Since the first conductive MOF is successfully synthesized in 2009, considerable progress has been achieved for the development of conductive MOFs, allowing their use in diverse applications for electrochemical energy storage. Among those applications, supercapacitors have received great interest because of their high power density, fast charging ability, and excellent cycling stability.

Structural Forces in Ionic Liquids: The Role of Ionic Size Asymmetry.

Ionic liquids (ILs) are charged fluids composed of anions and cations of different size and shape. The ordering of charge and density in ILs confined between charged interfaces underlies numerous applications of IL electrolytes. Here, we analyze the screening behavior and the resulting structural forces of a representative IL confined between two charge-varied plates.

Salt-in-Ionic-Liquid Electrolytes: Ion Network Formation and Negative Effective Charges of Alkali Metal Cations.

Salt-in-ionic liquid electrolytes have attracted significant attention as potential electrolytes for next generation batteries largely due to their safety enhancements over typical organic electrolytes. However, recent experimental and computational studies have shown that under certain conditions alkali cations can migrate in electric fields as if they carried a net negative effective charge. In particular, alkali cations were observed to have negative transference numbers at small mole fractions of alkali-metal salt that revert to the expected net positive transference numbers at large mole fractions.

Structural effects in nanotribology of nanoscale films of ionic liquids confined between metallic surfaces.

Room Temperature Ionic Liquids (RTILs) attract significant interest in nanotribology. However, their microscopic lubrication mechanism is still under debate. Here, using non-equilibrium molecular dynamics simulations, we investigate the lubrication performance of ultra-thin (<2 nm) films of [CMIM] [NTf] confined between plane-parallel neutral surfaces of Au(111) or Au(100).