Chemistry occurring at or near the surfaces of aqueous droplets and thin films in the atmosphere influences air quality and climate. Molecular dynamics simulations are becoming increasingly useful for gaining atomic-scale insight into the structure and reactivity of aqueous interfaces in the atmosphere. Here we review simulation studies of atmospherically relevant aqueous liquid-air interfaces, with an emphasis on ions that play important roles in the chemistry of atmospheric aerosols. In addition to surveying results from simulation studies, we discuss challenges to the refinement and experimental validation of the methodology for simulating ion adsorption to the air-water interface, and recent advances in elucidating the driving forces for adsorption. We also review the recent development of a dielectric continuum theory that is capable of reproducing simulation and experimental data on ion behavior at aqueous interfaces.
Responsive foams and interfaces, are interesting for active materials that respond to external stimuli. We have used the photochromic reaction of a spiropyran surfactant to render interfacial, rising bubble as well as foaming properties active to light stimuli. In order to address the air-water interface, we have applied sum-frequency generation (SFG) which has provided qualitative information on the surface excess and the interfacial charging state as a function of light irradiation and pH. Under blue light, the surfactant forms a closed ring spiro form (SP), whereas under dark conditions the…
Aqueous suspensions of Laponite, a system composed of disk-like nanoparticles, are found to develop optical birefringence over several days, well after the suspensions solidified due to jamming. The optical anisotropy is particularly enhanced near the air Laponite suspension interface over length-scales of several millimetres, which is beyond five orders of magnitude larger than the particle length scale, suggestive of large scale ordering influenced by the interface. The orientational order increases with time and is always greater for higher concentration of salt, higher concentration of Lap…
We report a simple route to form robust, inorganic, semi-permeable compartments composed of montmorillonite, a natural plate-like clay mineral that occurs widely in the environment. Mechanical forces due to shear in a narrow gap assemble clay nanoplates from an aqueous suspension onto air bubbles. Translucent vesicles suspended in a single-phase liquid are produced when the clay-covered air bubbles are exposed to a variety of water-miscible organic liquids. These vesicles of clay are mechanically robust and are stable in water and other liquids. The formation of clay vesicles can be described …
Recent reports on the formation of hydrogen peroxide (H$_2$O$_2$) in water microdroplets produced via pneumatic spraying or capillary condensation have garnered significant attention. How covalent bonds in water could break under such conditions challenges our textbook understanding of physical chemistry and the water substance. While there is no definitive answer, it has been speculated that ultrahigh electric fields at the air-water interface are responsible for this chemical transformation. Here, we resolve this mystery via a comprehensive experimental investigation of H$_2$O$_2$ formation …
The Jones-Ray effect is an anomalous minimum in the surface tension of aqueous electrolytes at millimolar salt concentrations. We experimentally demonstrated that intentionally added ionic surfactants induce the Jones-Ray effect. The one-dimensional Poisson-Boltzmann theory, including the effect of surfactant adsorption and salt depletion, excellently agrees with the obtained experimental data. All the parameters of the ion-specific surface affinities used in the theory are consistent with previous experiments. These results strongly suggest that the Jones-Ray effect observed so far has been i…
We have developed a method to produce aqueous microdroplets in an oil phase, based on the periodic extraction of a pending droplet across the oil/air interface. This interface forms a capillary trap inside which a droplet can be captured and detached. This process is found to be capillary- based and quasi-static. The droplet size and emission rate are independently governed by the injected volume per cycle and the extraction frequency. We find that the minimum droplet diameter is close to the injection glass capillary diameter and that variations in surface tension moderately perturb the dropl…
The formation of smart emulsions or foams whose stability can be controlled on-demand by switching external parameters is of great interest for basic research and applications. An emerging group of smart stabilizers are microgels, which are nano- and micro-sized, three-dimensional polymer networks that are swollen by a good solvent. In the last decades, the influence of various external stimuli on the two-dimensional phase behavior of microgels at air- and oil-water interfaces has been studied. However, the impact of the top-phase itself has been barely considered. Here, we present data that d…
The magnitude of the pH of the surface of water continues to be a contentious topic in the physical chemistry of aqueous interfaces. Recent theoretical studies have shown little or no preference for the proton to be at the surface compared to the bulk\cite{baer2014toward}. Using ab-initio molecular dynamics simulations, we revisit the propensity of the excess proton for the air-water interface with a particular focus on the role of instantaneous liquid interfaces. We find a much a stronger propensity of the proton for the surface of water. The enhanced water structuring around the proton resul…
The structure of the transient layer at the interface between air and the aqueous solution of silica nanoparticles with the size distribution of particles that has been determined from small-angle scattering has been studied by the X-ray reflectometry method. The reconstructed depth profile of the polarizability of the substance indicates the presence of a structure consisting of several layers of nanoparticles with the thickness that is more than twice as large as the thickness of the previously described structure. The adsorption of 1,2-distearoyl-sn-glycero-3-phosphocholine molecules at the…
Binding and phase behavior of oppositely charged polyelectrolytes and surfactants were studied in aqueous bulk solutions and at air-water interfaces. In particular, we have investigated the polyanion poly(sodium 4-styrenesulfonate) (NaPSS) and the cationic surfactants dodecyltrimethylammonium bromide (C$_{12}$TAB), tetradecyltrimethylammonium bromide (C$_{14}$TAB) and cetyltrimethylammonium bromide (C$_{16}$TAB). In order to reveal surfactant/polyelectrolyte binding, aggregation and phase separation of the mixtures, we have varied the NaPSS concentration systematically and have kept the surfac…
Charged colloidal monolayers at the interface between water and air (or oil) are used in a large number of chemical, physical and biological applications. Although a considerable experimental and theoretical effort has been devoted in the past few decades to investigate such monolayers, some of their fundamental properties are not yet fully understood. In this paper, we model charged colloidal monolayers as a continuum layer of finite thickness, with separate charge distribution on the water and air sides. The electrostatic surface free-energy and surface pressure are calculated via the chargi…
Supercooling of aqueous solutions below their melting point without any crystallization is a fundamentally and practically important physical phenomenon with numerous applications in biopreservation and beyond. Under normal conditions, heterogeneous nucleation mechanisms critically prohibit the simultaneous long-term (> 1 week), large volume (> 1 ml) and low temperatures (< -10 oC) supercooling of aqueous solutions. Here, in order to overcome this bottleneck and enable novel and practical supercooling applications, we report on the use of surface sealing of water by an oil phase to drastically…
Responsive poly-N-isopropylacrylamide-based microgels are commonly used as model colloids with soft repulsive interactions. It has been shown that the microgel-microgel interaction in solution can be easily adjusted by varying the environmental parameters, e.g., temperature, pH, or salt concentration. Furthermore, microgels readily adsorb to liquid-gas and liquid-liquid interfaces forming responsive foams and emulsions that can be broken on-demand. In this work, we explore the interactions between microgel monolayers at the air-water interface and a hard colloid in the water. Force-distance cu…
X-ray reflectivity and fluorescence near total reflection experiments were performed to examine the affinities of divalent ions ($\mathrm{Ca^{2+}}$ and $\mathrm{Ba^{2+}}$) from aqueous solution to a charged phosphatidic-acid (PA) surface. A phospholipid (1,2-Dimyristoyl-sn-Glycero-3-Phosphate, DMPA), spread as a monolayer at the air/water interface, was used to form and control the charge density at the interface. We find that for solutions of the pure salts (i.e., $\mathrm{CaCl_{2}}$ and $\mathrm{BaCl_{2}}$), the number of bound ions per DMPA at the interface is saturated at concentrations th…
Elucidating contact electrification mechanism of water
École Polytechnique Fédérale de Lausanne (EPFL)（洛桑联邦理工学院）；Karlsruhe Institute of Technology（卡尔斯鲁厄理工学院）；University of Stuttgart（斯图加特大学）；University of Washington（华盛顿大学）
