Density functional theory study of doped coronene and circumcoronene as anode materials in lithium-ion batteries.

Density functional theory calculations are carried out to investigate the adsorption properties of Li+ and Li on twenty-four adsorbents obtained by replacement of C atoms of coronene (C24H12) and circumcoronene (C54H18) by Si/N/BN/AlN units. The molecular electrostatic potential (MESP) analysis show that such replacements lead to an increase of the electron-rich environments in the molecules. Li+ is relatively strongly adsorbed on all adsorbents. The adsorption energy of Li+ (Eads-1) on all adsorbents is in the range of - 42.47 (B12H12N12) to - 66.26 kcal/mol (m-C22H12BN). Our results indicate a stronger interaction between Li+ and the nanoflakes as the deepest MESP minimum of the nanoflakes becomes more negative. A stronger interaction between Li+ and the nanoflakes pushes more electron density toward Li+. Li is weakly adsorbed on all adsorbents when compared to Li+. The adsorption energy of Li (Eads-2) on all adsorbents is in the range of - 3.07 (B27H18N27) to - 47.79 kcal/mol (C53H18Si). Assuming the nanoflakes to be an anode for the lithium-ion batteries, the cell voltage (Vcell) is predicted to be relatively high (> 1.54 V) for C24H12, C12H12Si12, B12H12N12, C27H18Si27, and B27H18N27. The Eads-1 data show only a small variation compared to Eads-2, and therefore, Eads-2 has a strong effect on the changes in Vcell.

Interfacial properties of the brine + carbon dioxide + oil + silica system.

Molecular dynamics simulations of the H2O + CO2 + aromatic hydrocarbon and H2O + CO2 + benzene + silica (hydrophilic) systems are performed to gain insights into CO2-enhanced oil recovery (EOR) processes. For comparison purposes, an overview of the previous simulation studies of the interfacial properties of the brine + CO2 + alkane + silica system is also presented. In general, the water contact angle (CA) of the H2O + CO2 + silica (hydrophilic) system increased with pressure and decreased with temperature. The CAs of the H2O + hydrocarbon + silica (hydrophilic) system are not significantly affected by temperature and pressure. The simulated CAs were in the ranges of about 58°-77° and 81°-93° for the H2O + hexane + silica (hydrophilic) and the H2O + aromatic hydrocarbon + silica (hydrophilic) systems, respectively. In general, these CAs were not significantly influenced by the addition of CO2. The simulated CAs were in the ranges of about 51.4°-95.0°, 69.1°-86.0°, and 72.0°-87.9° for the brine + CO2 + silica (hydrophilic), brine + hexane + silica (hydrophilic), and brine + CO2 + hexane + silica (hydrophilic) systems, respectively. All these CAs increased with increasing NaCl concentration. The adhesion tension of the brine + silica (hydrophilic) system in the presence of CO2 and/or hexane decreased with increasing salt concentration. The simulated CAs were in the range of about 117°-139° for the H2O + alkane + silica (hydrophobic) system. These CAs are increased by the addition of CO2. At high pressures, the distributions of H2O normal to the silica (hydrophobic) surface in the droplet region of the H2O + silica system were found to be strongly affected by the presence of CO2. These insights might be key for optimizing the performance of the miscible CO2 water-alternating-gas injection schemes widely used for EOR.

Transport of Heptane Molecules across Water-Vapor Interfaces Laden with Surfactants.

Molecular transport across liquid-vapor interfaces covered by surfactant monolayers plays a key role in applications such as fire suppression by foams. The molecular understanding of such transport, however, remains incomplete. This work uses molecular dynamics simulations to investigate the heptane transport across water-vapor interfaces populated with sodium dodecyl sulfate (SDS) surfactants. Heptane molecules' potential of mean force (PMF) and local diffusivity profiles across SDS monolayers with different SDS densities are calculated to obtain heptane's transport resistance. We show that a heptane molecule experiences a finite resistance as it crosses water-vapor interfaces covered by SDS. Such interfacial transport resistance is contributed significantly by heptane molecules' high PMF in the SDS headgroup region and their slow diffusion there. This resistance increases linearly as the SDS density rises from zero but jumps as the density approaches saturation when its value is equivalent to that afforded by a 5 nm thick layer of bulk water. These results are understood by analyzing the micro-environment experienced by a heptane molecule crossing SDS monolayers and the local perturbation it brings to the monolayers. The implications of these findings for the design of surfactants to suppress heptane transport through water-vapor interfaces are discussed.

Interfacial properties of the hexane + carbon dioxide + water system in the presence of hydrophilic silica.

Molecular dynamics simulations were conducted to study the interfacial behavior of the CO2 + H2O and hexane + CO2 + H2O systems in the presence of hydrophilic silica at geological conditions. Simulation results for the CO2 + H2O and hexane + CO2 + H2O systems are in reasonable agreement with the theoretical predictions based on the density functional theory. In general, the interfacial tension (IFT) of the CO2 + H2O system exponentially (linearly) decreased with increasing pressure (temperature). The IFTs of the hexane + CO2 + H2O (two-phase) system decreased with the increasing mole fraction of CO2 in the hexane/CO2-rich phase xCO2 . Here, the negative surface excesses of hexane lead to a general increase in the IFTs with increasing pressure. The effect of pressure on these IFTs decreased with increasing xCO2 due to the positive surface excesses of carbon dioxide. The simulated water contact angles of the CO2 + H2O + silica system fall in the range from 43.8° to 76.0°, which is in reasonable agreement with the experimental results. These contact angles increased with pressure and decreased with temperature. Here, the adhesion tensions are influenced by the variations in fluid-fluid IFT and contact angle. The simulated water contact angles of the hexane + H2O + silica system fall in the range from 58.0° to 77.0° and are not much affected by the addition of CO2. These contact angles increased with pressure, and the pressure effect was less pronounced at lower temperatures. Here, the adhesion tensions are mostly influenced by variations in the fluid-fluid IFTs. In all studied cases, CO2 molecules could penetrate into the interfacial region between the water droplet and the silica surface.

Interfacial behavior of the decane + brine + surfactant system in the presence of carbon dioxide, methane, and their mixture.

Molecular dynamics simulations are carried out to get insights into the interfacial behavior of the decane + brine + surfactant + CH4 + CO2 system at reservoir conditions. Our results show that the addition of CH4, CO2, and sodium dodecyl sulfate (SDS) surfactant at the interface reduces the IFTs of the decane + water and decane + brine (NaCl) systems. Here the influence of methane was found to be less pronounced than that of carbon dioxide. As expected, the addition of salt increases the IFTs of the decane + water + surfactant and decane + water + surfactant + CH4/CO2 systems. The IFTs of these surfactant-containing systems decrease with temperature and the influence of pressure is found to be less pronounced. The atomic density profiles show that the sulfate head groups of the SDS molecules penetrate the water-rich phase and their alkyl tails are stretched into the decane-rich phase. The sodium counterions of the surfactant molecules are located very close to their head groups. Furthermore, the density profiles of water and salt ions are hardly affected by the presence of the SDS molecules. However, the interfacial thickness between water and decane/CH4/CO2 molecules increases with increasing surfactant concentration. An important result is that the enrichment of CH4 and/or CO2 in the interfacial region decreases with increasing surfactant concentration. These results may be useful in the context of the water-alternating-gas approach that has been utilized during CO2-enhanced oil recovery operations.

Bulk and Interfacial Properties of the Decane + Water System in the Presence of Methane, Carbon Dioxide, and Their Mixture.

Molecular dynamics simulations are carried out to study the two-phase behavior of the n-decane + water system in the presence of methane, carbon dioxide, and their mixture under reservoir conditions. The simulation studies were complemented by theoretical modeling using the perturbed-chain statistical associating fluid theory (PC-SAFT) equation of state (EoS) and density gradient theory. Our results show that the presence of methane and carbon dioxide decreases the interfacial tension (IFT) of the decane + water system. In general, the IFT increases with increasing pressure and decreasing temperature for the methane + decane + water and carbon dioxide + decane + water systems, similar to what has been found for the corresponding decane + water system. The most important finding of this study is that the presence of carbon dioxide decreases the IFT of the methane + decane + water system. The atomic density profiles provide evidence of the local accumulation of methane and carbon dioxide at the interface, in most of the studied systems. The results of this study show the preferential dissolution in the water-rich phase and enrichment at the interface for carbon dioxide in the methane + carbon dioxide + decane + water system. This indicates the preferential interaction of water with carbon dioxide relative to methane and decane. Notably, there is an enrichment of the interface by decane at high mole fractions of methane in the methane/decane-rich or methane/carbon dioxide/decane-rich phase. Overall, the solubility of methane and carbon dioxide in the water-rich phase increases with increasing pressure and temperature. Additionally, we find that the overall performance of the PC-SAFT EoS and the cubic-plus-association EoS is similar with respect to the calculation of bulk and interfacial properties of these systems.

Sorption and Diffusion of Methane and Carbon Dioxide in Amorphous Poly(alkyl acrylates): A Molecular Simulation Study.

Molecular simulations were carried out to understand the structural features and the sorption and diffusion behavior of methane and carbon dioxide in amorphous poly(alkyl acrylates) in the temperature range of 300-600 K. The hybrid Monte Carlo/molecular dynamics approach was employed to address the effects of polymer swelling and framework flexibility on the gas sorption. Simulations show that the glass-transition temperature decreases with the side-chain length of poly(alkyl acrylate), consistent with experiments. This is due to the fact that the shielding of the polar ester groups increases with the side-chain length. The simulated sorption isotherms for methane and carbon dioxide were in agreement with the experimental data. The polymer swelling becomes more pronounced, especially in the case of sorption of carbon dioxide. A significant swelling occurs, possibly because of the greater interaction between carbon dioxide and the polar ester groups in the polymers. The uptake of methane and carbon dioxide by poly(alkyl acrylates) generally increases with the side-chain length. Our simulations confirm the experimental findings that the diffusion coefficients of methane and carbon dioxide in poly(alkyl acrylates) increase with the side-chain length. Interestingly, the activation energies of gas diffusion decrease with the side-chain length. The diffusion coefficients of the penetrants have an exponential relationship with the void fraction, which is in agreement with the free volume theory.

Bulk and interfacial properties of decane in the presence of carbon dioxide, methane, and their mixture.

Molecular dynamics simulations were performed to study the bulk and interfacial properties of methane + n-decane, carbon dioxide + n-decane, and methane + carbon dioxide + n-decane systems under geological conditions. In addition, theoretical calculations using the predictive Peng-Robinson equation of state and density gradient theory are carried out to compare with the simulation data. A key finding is the preferential dissolution in the decane-rich phase and adsorption at the interface for carbon dioxide from the methane/carbon dioxide mixture. In general, both the gas solubility and the swelling factor increase with increasing pressure and decreasing temperature. Interestingly, the methane solubility and the swelling of the methane + n-decane system are not strongly influenced by temperature. Our results also show that the presence of methane increases the interfacial tension (IFT) of the carbon dioxide + n-decane system. Typically, the IFT of the studied systems decreases with increasing pressure and temperature. The relatively higher surface excess of the carbon dioxide + n-decane system results in a steeper decrease in its IFT as a function of pressure. Such systematic investigations may help to understand the behavior of the carbon dioxide-oil system in the presence of impurities such as methane for the design and operation of carbon capture and storage and enhanced oil recovery processes.

Effect of Ion Valency on the Properties of the Carbon Dioxide-Methane-Brine System.

Molecular dynamics simulations and theoretical analysis were carried out to study the bulk and interfacial properties of carbon dioxide-methane-water and carbon dioxide-methane-brine systems under geological conditions. The density gradient theory with the bulk phase properties estimated using the cubic-plus-association (CPA) equation of state (EoS) can well describe the increase in the interfacial tension (IFT) of the CO2-water system in the presence of methane. The theoretical estimates of species mole fractions in the carbon dioxide-methane-water system are in good quantitative agreement with the experimental results. Furthermore, simulations of carbon dioxide-methane-brine system show that the IFT of the CaCl2 case is generally higher than that of the NaCl case. This is probably due to the stronger hydration of Ca2+ ions and their stronger repulsion from the interface compared to Na+. While the overall shape of the ionic profiles is not much affected by the ion type, the water profiles show a local enrichment at the interface in the system with CaCl2. In contrast to the case of NaCl, the slopes of the plots of IFT vs CaCl2 concentration are dependent on temperature. Species mole fractions in the carbon dioxide-methane-brine system predicted by combining the CPA EoS with the Debye-Hückel electrostatic term are in good agreement with simulation results.

Molecular Dynamics Simulation Study of Carbon Dioxide, Methane, and Their Mixture in the Presence of Brine.

We perform molecular dynamics simulation study of CO2, methane, and their mixture in the presence of brine over a broad range of temperature (311-473 K), pressure (up to about 100 MPa), and NaCl concentration (up to about 14 wt %). The general decrease in the interfacial tension (IFT) values of the CH4-brine system with pressure and temperature is similar to that obtained for the corresponding CH4-water system. The IFT of methane and brine is a linearly increasing function of salt concentration, and the resulting slopes are dependent on the pressure. A similar behavior as methane is observed for such systems containing CO2 and CO2-CH4 mixture. The IFT of CO2 and brine increases linearly with increasing salt content; however, the resulting slopes are independent of pressure. The simulations show that the presence of CO2 decreases the IFT values of the CH4-water and CH4-brine systems, but the degree of reduction depends on the amount of CO2 in each sample, which is consistent with experimental evidence. These IFT values show a linear correlation with the amount of CO2, and the resulting slopes are dependent on the temperature and pressure. Furthermore, our results for the mole fractions of the different species in the CO2-CH4-water system at 323 K and 9 MPa are in agreement with those of experiments. The mole fractions of methane and CO2 in the water-rich phase decrease with increasing salt concentration, whereas that of H2O in the methane- or CO2-rich phases remains almost unaffected in all of the studied cases. Our results could be useful because of the importance of carbon dioxide sequestration and shale gas production.

Complexation Behavior of Polyelectrolytes and Polyampholytes.

We perform grand canonical Monte Carlo simulations to study the pH titrations of isolated polyampholytes and polyelectrolyte-polyampholyte complexes in dilute solutions. Our simulations indicate that the electrostatic interactions promote the coexistence of opposite charges along the polyampholyte chain during titration. The repulsion between excess charges typically dominates the electrostatic interaction and leads to polymer stretching. Salt ions can screen the repulsion between excess charges as well as the fluctuation-induced attraction between opposite charges, and therefore make the variation between titration curves of polyampholytes and the ideal (no electrostatic interactions) curves less significant. We observe that this screening of charge repulsion decreases the chain size. The presence of pearl-necklace configuration of polyampholytes is diminished by the addition of salt. Similar simulations for the polyelectrolyte-polyampholyte system show that the resulting complexes are generally stable in the low pH region. In comparison to ideal case, electrostatic interactions strongly influence the acid-base properties of polyampholyte chains in the adsorbed state by reducing the presence of the coexistence domain of both positive and negative charges in the titration curves. We attribute the complex formation between polyelectrolyte and polyampholyte chains in the high pH region to, e.g., the high salt content. The pH variation leads to abrupt transition between adsorbed and desorbed states. Independent of charge sequence, a polyampholyte chain in a complex is usually located at one of the ends of the polyelectrolyte chain.

Conformational transitions of a weak polyampholyte.

Using grand canonical Monte Carlo simulations of a flexible polyelectrolyte where the charges are in contact with a reservoir of constant chemical potential given by the solution pH, we study the behavior of weak polyelectrolytes in poor and good solvent conditions for polymer backbone. We address the titration behavior and conformational properties of a flexible diblock polyampholyte chain formed of two oppositely charged weak polyelectrolyte blocks, each containing equal number of identical monomers. The change of solution pH induces charge asymmetry in a diblock polyampholyte. For diblock polyampholyte chains in poor solvents, we demonstrate that a discontinuous transition between extended (tadpole) and collapsed (globular) conformational states is attainable by varying the solution pH. The double-minima structure in the probability distribution of the free energy provides direct evidence for the first-order like nature of this transition. At the isoelectric point electrostatically driven coil-globule transition of diblock polyampholytes in good solvents is found to consist of different regimes identified with increasing electrostatic interaction strength. At pH values above or below the isoelectric point diblock chains are found to have polyelectrolyte-like behavior due to repulsion between uncompensated charges along the chain.

Meconium peritonitis secondary to torsion of fallopian tube cyst and transient central diabetes insipidus in a preterm infant.

Meconium peritonitis is a sterile chemical peritonitis caused by peritoneal seeding of meconium from an antenatal gastrointestinal perforation. We report a 32-week preterm female neonate who developed meconium peritonitis due to bowel perforation, secondary to a twisted left fallopian tube mass, which was excised and confirmed by histopathology. This association has not been reported earlier. The infant also developed transient central diabetes insipidus, a very rare condition in a preterm neonate.