Grand canonical Monte Carlo (GCMC) simulations are employed to study the selective electrosorption of ions from a mixture of symmetric and asymmetric electrolytes confined in pores and results are compared to experimental observations obtained via cyclic voltammetry and batch electrosorption equilibrium experiments. GCMC simulations have the advantage over other Monte Carlo methods to unambiguously quantify the total number of ions in the pore solution. The exclusion parameter and selectivity factor are used to evaluate the selective capacity of pores toward different ionic species under various conditions. The number of coions inside the pore solution is determined by the proportion of different counterions present in the double-layer region. Because of the competitive effects resulting from asymmetries in charge and size associated with different ions, the electrosorption selectivity of small monovalent over large divalent counterions first decreases with increasing surface charge, passes through a minimum, and then increases with further increase in surface charge. At low and moderate surface charge densities, the fact that large divalent counterions preferentially screen the surface charge has a strong effect on pore occupancy; whereas at a very high surface charge density, size-exclusion effects dominate and determine the accessibility of different ions into the pores. Therefore, electrosorption selectivity of ions from a mixture of electrolytes could, in principle, be achieved via tuning the electrical double-layer formation inside the pores through the regulation of surface charge tailored for different ion characteristics. The findings of this work provide important information relevant to ion selectivity during separation processes and energy storage in supercapacitors.
Canonical Monte Carlo (CMC) simulations are employed in this work in order to study the structure of the electrical double layer (EDL) near discretely charged planar surfaces in the presence of symmetric and asymmetric indifferent electrolytes within the framework of a primitive model. The effects of discreteness and strength of surface charge, charge asymmetry, and size asymmetry are specific focuses of this work. The CMC simulation protocol is initially tested against the classical theory, the modified Gouy-Chapman (GC) theory, in order to assess the reliability of the simulation results. The CMC simulation results and the predictions of the classical theory show good agreement for 1:1 electrolytes and low surface charge, at which conditions the GC theory is valid. Simulations with symmetric and asymmetric electrolytes and mixtures of the two demonstrate that size plays an important role in determining the species present in the EDL and how the surface charge is screened. A size-exclusion effect could be consistently detected. Although it is energetically favorable that higher-valence ions screen the surface charge, their larger size prevents them from getting close to the surface. Smaller ions with lower valences perform the screening of the charge, resulting in higher local concentrations of small ions close to the surface. The simulations also showed that the strength of the surface charge enhances the size-exclusion effect. This effect will definitely affect the magnitude of the forces between interacting charged surfaces.
The formation of the electrical double layer (EDL) in the presence of trivalent and monovalent ions inside a slit-type nanopore was simulated via the canonical Monte Carlo method using a primitive model. In large pores, the distribution of ionic species is similar to that observed in an isolated planar double layer. Screening of surface charge is determined by the competitive effects between ion size and charge asymmetry of the counterions. On the other hand, as the pore size approaches the dimension of the ionic species, phenomena such as EDL overlapping become enhanced by ion-size effects. Simulation results demonstrate that EDL overlapping is not only a function of such parameters as ionic strength and surface charge density, but also a function of the properties of the ionic species involved in the EDL. Furthermore, charge inversion can be observed under certain conditions when dealing with mixtures of asymmetric electrolytes. This phenomenon results from strong ion-ion correlation effects and the asymmetries in size and charge of ionic species, and is most significant in the case of trivalent counterions with larger diameters. The simulation results provide insights into the fundamental mechanisms behind the formation of EDL within nanopores as determined by pore size and by the properties of ionic species present in solution. The findings of this work are relevant to ion sorption and transport within nanostructured materials.
Unfavorable aggregation and deposition of colloidal particles in natural and engineered systems is still a subject of debate. Complicating factors such as surface roughness, secondary minimum aggregation, and the nature of discrete surface charge and surface potential make it difficult to attribute a specific cause to these phenomena. The presence of surface charge heterogeneity and its influence on interaction forces, which are responsible for aggregation and deposition, are studied in this work through the application of atomic force microscopy (AFM). Force-volume-mode AFM was used to map interaction forces on a surface and relate them to surface charge heterogeneities. The experimental system consisted of a silica plate and a standard silicon nitride AFM tip. Copper ions were used for sorption on the silica surface in order to modify the surface charge and cause charge reversal. Different concentrations of copper ions were selected to identify conditions of partial coverage of the silica surface. The pH and ionic strength of the solutions were varied, and the extension of the surface charge modification and its influence on the resulting interaction forces were monitored via AFM force measurements. Depending on the pH and ionic strength, the interaction force was found to change at certain regions on the surface from attraction to either weak or strong repulsion. Force imaging allowed the visual localization of zones of strong repulsive interaction that diminished in size with increasing ionic strength. X-ray photoelectron spectroscopy analysis was used to confirm the presence of copper on the surface. Local charge differences on a surface result in local differences in surface forces, not only in magnitude but also in direction. This behavior may explain the aggregation, deposition, and transport of colloidal particles under unfavorable chemical conditions.
A pilot-scale, three-phase continuous-jet hydrate reactor, developed to produce CO2 hydrate for ocean sequestration, was tested both in the laboratory and at sea. A 72-L pressure vessel was used for laboratory tests; field experiments were performed with a remotely operated vehicle at depths between 1200 and 2000 m off the coast of Monterey, CA. Rapid production of a consolidated sinking CO2–hydrate composite paste was achieved in both settings. The vertical and lateral movement of the extruded hydrate was monitored by the high-definition television camera mounted on the vehicle and with a 675-kHz scanning sonar, along with dissolution rates and associated temperature and pH changes during the injection operations. It was observed that globules of unconverted liquid CO2 occluded in the structure of the hydrate composite largely determine the hydrate composite behavior in the ocean by providing sites for accelerated dissolution, thereby affecting the CO2–hydrate particle orientation, shape, lifetime, and sinking rate. Model calculations predict that large-scale releases of these particles (at a CO2 injection rate of ∼100 kg/s) should show a descent depth of nearly 1000 m below their release point, as a result of plume dynamics and the increase in density caused by the CO2 dissolution into the surrounding ocean water.
Canonical Monte Carlo simulations of the interaction between a uniformly charged spherical particle and a discretely charged planar surface in solutions of symmetric and asymmetric electrolytes were performed. To assess the nature of the interactions, the force exerted on the colloidal particle perpendicular to the planar surface was calculated. Attractive minima in the interaction force between the similarly charged surfaces reveal the occurrence of two phenomena: long-range attraction of electrostatic origin and short-range attraction due to depletion effects. The degree of electrostatic coupling determines the magnitude and range of like-charge attraction between the two surfaces.
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