Molecular Density Fluctuations Control Solubility and Diffusion for Confined Aqueous Hydrogen.

Hydrogen's contribution to a sustainable energy transformation requires intermittent storage technologies, e.g., underground hydrogen storage (UHS). Toward designing UHS sites, atomistic molecular dynamics (MD) simulations are used here to quantify thermodynamic and transport properties for confined aqueous H2. Slit-shaped pores of width 10 and 20 Šare carved out of kaolinite. Within these pores, water yields pronounced hydration layers. Molecular H2 distributes along these hydration layers, yielding solubilities up to ∼25 times those in the bulk. Hydrogen accumulates near the siloxane surface, where water density fluctuates significantly. On the contrary, a dense hydration layer forms on the gibbsite surface, which is, for the most part, depleted of H2. Although confinement reduces water mobility, the diffusion of aqueous H2 increases as the kaolinite pore width decreases, also a consequence of water density fluctuations. These results relate to H2 permeability in underground hydrogen storage sites.

Molecular Interactions of Perfluorinated and Branched Fluorine-Free Surfactants at Interfaces: Insights from a New Reliable Force Field.

Per- and polyfluoroalkyl substances (PFAS) constitute a class of synthetic compounds with exceptional interfacial properties. Their widespread use in many industrial applications and consumer products, combined with their remarkable chemical and thermal stability, has led to their ubiquitous presence in environmental matrices, including surface water and groundwater. To replace PFAS with fluorine-free surfactants, it is necessary first to develop a deep molecular-level understanding of the mechanisms responsible for the exceptional properties of PFAS. For instance, it has been shown that fluorine-free surfactants with highly branched or methylated chains can achieve low surface tensions at air-water interfaces and can provide highly hydrophobic surface coatings. Although molecular simulations combined with experiments are promising for uncovering these mechanisms, the reliability of simulation results depends strongly on the accuracy of the force fields implemented. At the moment, atomistic force fields are not available to describe PFAS in a variety of environments. Ab initio methods could help fill this knowledge gap, but they are computationally demanding. As an alternative, ab initio calculations could be used to develop accurate force fields for atomistic simulations. In this work, a new algorithm is proposed, which, built from accurate ab initio calculations, yields force fields for perfluorinated sulfonic and perfluoroalkyl acids. The accuracy of the new force field was benchmarked against solvation free energy and interfacial tension data. The new force fields were then used to probe the interfacial behavior of the PFAS surfactants. The interfacial properties observed in our simulations were compared with those manifested by two branched fluorine-free surfactants. The good agreement achieved with experiments and ab initio calculations suggests that the proposed protocol could be implemented to study other perfluorinated substances and help in the design of fluorine-free surfactants for targeted applications.

Mesoscale Simulations Reveal How Salt Influences Clay Particles Agglomeration in Aqueous Dispersions.

The aggregation of clay particles is an everyday phenomenon of scientific and industrial relevance. However, it is a complex multiscale process that depends delicately on the nature of the particle-particle and particle-solvent interactions. Toward understanding how to control such phenomena, a multiscale computational approach is developed, building from molecular simulations conducted at atomic resolution to calculate the potential of mean force (PMF) profiles in both pure and saline water environments. We document how it is possible to use such a model to develop a fundamental understanding concerning the mechanism of particle aggregation. For example, using molecular dynamics simulations conducted at the mesoscale in implicit solvents, it is possible to quantify the size and shape of clay aggregates as a function of system conditions. The approach is used to emphasize the role of salt concentration, which directly affects the potentials of the mean forces between kaolinite particles. While particle agglomeration in pure water yields large aggregates, the presence of sodium chloride in the aqueous brine leads instead to a large number of small aggregates. These results are consistent with macroscopic experimental observations, suggesting that the simulation protocol developed could be relevant for preventing pore blocking in heterogeneous porous matrixes.

Understanding the effect of moderate concentration SDS on CO2 hydrates growth in the presence of THF.

Hypothesis Additives like Tetrahydrofuran (THF) and Sodium Dodecylsulfate (SDS) improve Carbon Dioxide (CO2) hydrates thermal stability and growth rate when used separately. It has been hypothesised that combining them could improve the kinetics of growth and the thermodynamic stability of CO2 hydrates. Simulations and Experiments We exploit atomistic molecular dynamics simulations to investigate the combined impact of THF and SDS under different temperatures and concentrations. The simulation insights are verified experimentally using pendant drop tensiometry conducted at ambient pressures and high-pressure differential scanning calorimetry. Findings Our simulations revealed that the combination of both additives is synergistic at low temperatures but antagonistic at temperatures above 274.1 K due to the aggregation of SDS molecules induced by THF molecules. These aggregates effectively remove THF and CO2 from the hydrate-liquid interface, thereby reducing the driving force for hydrates growth. Experiments revealed that the critical micelle concentration of SDS in water decreases by 20% upon the addition of THF. Further experiments in the presence of THF showed that only small amounts of SDS are sufficient to increase the CO2 storage efficiency by over 40% compared to results obtained without promoters. Overall, our results provide microscopic insights into the mechanisms of THF and SDS promoters on CO2 hydrates, useful for determining the optimal conditions for hydrate growth.

Synergistic effects between a non-ionic and an anionic surfactant on the micellization process and the adsorption at liquid/air surfaces.

Predicting the behaviour of solutions with surfactants of significantly different critical micelle concentration (CMC) values remains a challenge. The study of the molecular interactions within micelles and interfaces in surfactant combinations used in everyday products is essential to understand these complex systems. In this work, the equilibrium and dynamic surface tension in the presence of mixed non-ionic (tristyrylphenol ethoxylates) and anionic (sodium benzene sulfonate with alkyl chain lengths of C10-C13) surfactants, commonly encountered as delivery systems in agrochemicals, were studied and their CMC values were determined. For the surfactant mixtures, four molar ratios were examined: nEOT/nNaDDBS = 0.01, 0.1, 1, 4 and two different cases were analysed, the premixed and the add one by one surfactant. The surface tension for single surfactants stabilised quickly, while the mixtures needed a long time to reach equilibrium; up to 15 h for the premixed mixtures and 40 min when surfactants were added one by one. The CMC values for the nEOT/nNaDDBS = 0.01, 0.1 premixed surfactant mixtures were found to be in between the CMC values of the single surfactants, but those for the nEOT/nNaDDBS = 1 and 4 mixtures were lower than the CMCs of both single surfactants. Calculations based on the regular solution theory suggested that there are attractive forces in the mixed micelles and at the interface layers, while the supramolecular assemblies in the bulk (i.e., micelles) and at interfaces (surfactant films) are preferentially enriched in EOT.

Hop, Skip, and Jump: Hydrogen Molecular Transport through Amorphous Polyethylene Matrices Studied via Molecular Dynamics Simulations.

In the pursuit of advancing and diversifying energy technologies for a more sustainable future, the possibilities of hydrogen (H2) usage will broaden, as will our understanding of its containment materials. Polyethylene (PE) has a vast assortment of uses and applications, which are growing with demands for alternative energy possibilities. One use of PE liner is as a prime candidate for nonmetallic piping and pressurized type IV storage devices. Such applications require PE to effectively prevent H2 transport through containment systems. To study the molecular transport mechanism of hydrogen through polymeric barriers, a system containing hydrogen molecules absorbed within amorphous PE is modeled here using molecular dynamics simulations. The simulations are conducted within a range of temperatures that span the glass transition temperature of amorphous PE. The simulated PE displays bulk density, radius of gyration, and self-diffusion coefficient that are consistent with experimental data. The simulated trajectories are interrogated to study the movement of the guest gas molecules. The results show that the diffusion coefficients increase with temperature, as expected. However, the mobility of the PE chains is found to affect the mobility of absorbed H2 molecules to a much lower extent than it affects that of CH4 molecules because of the much smaller size of the former than of the latter guest. From a molecular perspective, a "hopping" mechanism is observed, according to which H2 molecules hop between one vacant free volume space to another within the polymer matrix, in combination with longer, straight, undisturbed "jumps" or "skips" along directions aligned with regions of ordered PE chains. This suggests that the orientation of the crystallites within the semicrystalline PE matrix affects the H2 containment. Implications of these findings toward PE usage as containment material are discussed.

Analyzing the Accuracy of Critical Micelle Concentration Predictions Using Deep Learning.

This paper presents a novel approach to predicting critical micelle concentrations (CMCs) by using graph neural networks (GNNs) augmented with Gaussian processes (GPs). The proposed model uses learned latent space representations of molecules to predict CMCs and estimate uncertainties. The performance of the model on a data set containing nonionic, cationic, anionic, and zwitterionic molecules is compared against a linear model that works with extended connectivity fingerprints (ECFPs). The GNN-based model performs slightly better than the linear ECFP model when there is enough well-balanced training data and achieves predictive accuracy that is comparable to published models that were evaluated on a smaller range of surfactant chemistries. We illustrate the applicability domain of our model using a molecular cartogram to visualize the latent space, which helps to identify molecules for which predictions are likely to be erroneous. In addition to accurately predicting CMCs for some surfactant classes, the proposed approach can provide valuable insights into the molecular properties that influence CMCs.

Understanding the Aggregation of Model Island and Archipelago Asphaltene Molecules near Kaolinite Surfaces using Molecular Dynamics.

The solubility of asphaltenes in hydrocarbons changes with pressure, composition, and temperature, leading to precipitation and deposition, thereby causing one of the crucial problems that negatively affects oil production, transportation, and processing. Because, in some circumstances, it might be advantageous to promote asphaltene agglomeration into small colloidal particles, molecular dynamics simulations were conducted here to understand the impacts of a chemical additive inspired by cyclohexane on the mechanism of aggregation of model island and archipelago asphaltene molecules in toluene. We compared the results in the presence and absence of a kaolinite surface at 300 and 400 K. Cluster size analyses, radial distribution functions, angles between asphaltenes, radius of gyration, and entropic and energetic calculations were used to provide insights on the behavior of these systems. The results show that the hypothetical additive inspired by cyclohexane promoted the aggregation of both asphaltenes. Structural differences were observed among the aggregates obtained in our simulations. These differences are attributed to the number of aromatic cores and side chains on the asphaltene molecules as well as to that of heteroatoms. For the island structure, aggregation in the bulk phase was less pronounced than that in the proximity of the kaolinite surface, whereas the opposite was observed for the archipelago structure. In both cases, the additive promoted stacking of asphaltenes, yielding more compact aggregates. The results provided insights into the complex nature of asphaltene aggregation, although computational approaches that can access longer time and larger size scales should be chosen for quantifying emergent meso- and macroscale properties of systems containing asphaltenes in larger numbers than those that can currently be sampled via atomistic simulations.

Geothermal Energy Impact Estimator: A software application for estimating the life-cycle environmental impacts of geothermal energy.

Geothermal energy is a renewable source of base-load power that is expected to play an important role in the transition to a low-carbon economy. In this article, we introduce a novel software application - named Geothermal Energy Impact Estimator - which computes the environmental impacts, including carbon emissions, of existing or future geothermal plants, using the Life Cycle Assessment (LCA) methodology. The software application is user-friendly and was designed to be used by geothermal companies and policy makers. We provide two specific use cases of the software application that represent existing plants in Iceland and in the UK.

Stochastic Cellular Automata Modeling of CO2 Hydrate Growth and Morphology.

Carbon dioxide (CO2) hydrates are important in a diverse range of applications and technologies in the environmental and energy fields. The development of such technologies relies on fundamental understanding, which necessitates not only experimental but also computational studies of the growth behavior of CO2 hydrates and the factors affecting their crystal morphology. As experimental observations show that the morphology of CO2 hydrate particles differs depending on growth conditions, a detailed understanding of the relation between the hydrate structure and growth conditions would be helpful. To this end, this work adopts a modeling approach based on hybrid probabilistic cellular automata to investigate variations in CO2 hydrate crystal morphology during hydrate growth from stagnant liquid water presaturated with CO2. The model, which uses free energy density profiles as inputs, correlates the variations in growth morphology to the system subcooling ΔT, i.e., the temperature deficiency from the triple CO2-hydrate-water equilibrium temperature under a given pressure, and properties of the growing hydrate-water interface, such as surface tension and curvature. The model predicts that when ΔT is large, parabolic needle-like or dendrite crystals emerge from planar fronts that deform and lose stability. In agreement with chemical diffusion-limited growth, the position of such planar fronts versus time follows a power law. In contrast, the tips of the emerging parabolic crystals steadily grow in proportion to time. The modeling framework is computationally fast and produces complex growth morphology phenomena under diffusion-controlled growth from simple, easy-to-implement rules, opening the way for employing it in multiscale modeling of gas hydrates.

Microscopic insights on clathrate hydrate growth from non-equilibrium molecular dynamics simulations.

Clathrate hydrates form and grow at interfaces. Understanding the relevant molecular processes is crucial for developing hydrate-based technologies. Many computational studies focus on hydrate growth within the aqueous phase using the 'direct coexistence method', which is limited in its ability to investigate hydrate film growth at hydrocarbon-water interfaces. To overcome this shortcoming, a new simulation setup is presented here, which allows us to study the growth of a methane hydrate nucleus in a system where oil-water, hydrate-water, and hydrate-oil interfaces are all simultaneously present, thereby mimicking experimental setups. Using this setup, hydrate growth is studied here under the influence of two additives, a polyvinylcaprolactam oligomer and sodium dodecyl sulfate, at varying concentrations. Our results confirm that hydrate films grow along the oil-water interface, in general agreement with visual experimental observations; growth, albeit slower, also occurs at the hydrate-water interface, the interface most often interrogated via simulations. The results obtained demonstrate that the additives present within curved interfaces control the solubility of methane in the aqueous phase, which correlates with hydrate growth rate. Building on our simulation insights, we suggest that by combining data for the potential of mean force profile for methane transport across the oil-water interface and for the average free energy required to perturb a flat interface, it is possible to predict the performance of additives used to control hydrate growth. These insights could be helpful to achieve optimal methane storage in hydrates, one of many applications which are attracting significant fundamental and applied interests.

Chemical Promoter Performance for CO2 Hydrate Growth: A Molecular Perspective.

Carbon dioxide (CO2) hydrates, which contain a relatively large amount of captured CO2 (almost 30 wt % of CO2 with the balance being water), represent a promising CO2 sequestration option for climate change mitigation. To facilitate CO2 storage via hydrates, using chemical additives during hydrate formation might help to expedite formation/growth rates, provided the additives do not reduce the storage capacity. Implementing atomistic molecular dynamics, we study the impact of aziridine, pyrrolidine, and tetrahydrofuran (THF) on the kinetics of CO2 hydrate growth/dissociation. Our simulations are validated via reproducing experimental data for CO2 and CO2 + THF hydrates at selected operating conditions. The simulated results show that both aziridine and pyrrolidine could perform as competent thermodynamic and kinetic promoters. Furthermore, aziridine seems to exceed pyrrolidine and THF in expediting the CO2 hydrate growth rates under the same conditions. Our analysis unveils direct correlations between the kinetics of CO2 hydrate growth and a combination of the free energy barrier for desorption of CO2 from the hydrate surface and the binding free energy of chemical additives adsorbed at the growing hydrate substrate. The detailed thermodynamic analysis conducted in both hydrate and aqueous phases reveals molecular-level mechanisms by which CO2 hydrate promoters are active, which could help to enable the implementation of CO2 sequestration in hydrate-bearing reservoirs.

Hydration Structures on γ-Alumina Surfaces With and Without Electrolytes Probed by Atomistic Molecular Dynamics Simulations.

A wide range of systems, both engineered and natural, feature aqueous electrolyte solutions at interfaces. In this study, the structure and dynamics of water at the two prevalent crystallographic terminations of gamma-alumina, [110] and [100], and the influence of salts─sodium chloride, ammonium acetate, barium acetate, and barium nitrate on such properties─were investigated using equilibrium molecular dynamics simulations. The resulting interfacial phenomena were quantified from simulation trajectories via atomic density profiles, angle probability distributions, residence times, 2-D density distributions within the hydration layers, and hydrogen bond density profiles. Analysis and interpretation of the results are supported by simulation snapshots. Taken together, our results show stronger interaction and closer association of water with the [110] surface, compared to [100], while ion-induced disruption of interfacial water structure was more prevalent at the [100] surface. For the latter, a stronger association of cations is observed, namely sodium and ammonium, and ion adsorption appears determined by their size. The differences in surface-water interactions between the two terminations are linked to their respective surface features and distributions of surface groups, with atomistic-scale roughness of the [110] surface promoting closer association of interfacial water. The results highlight the fundamental role of surface characteristics in determining surface-water interactions, and the resulting effects on ion-surface and ion-water interactions. Since the two terminations of gamma-alumina considered represent interfaces of significance to numerous industrial applications, the results provide insights relevant for catalyst preparation and adsorption-based water treatment, among other applications.

Wetting Properties of Clathrate Hydrates in the Presence of Polycyclic Aromatic Compounds: Evidence of Ion-Specific Effects.

Polycyclic aromatic hydrocarbons (PAHs) have attracted remarkable multidisciplinary attention due to their intriguing π-π stacking configurations, showing enormous opportunity for their use in a variety of advanced applications. To secure progress, detailed knowledge on PAHs' interfacial properties is required. Employing molecular dynamics, we probe the wetting properties of brine droplets (KCl, NaCl, and CaCl2) on sII methane-ethane hydrate surfaces immersed in various oil solvents. Our simulations show synergistic effects due to the presence of PAHs compounded by ion-specific effects. Our analysis reveals phenomenological correlations between the wetting properties and a combination of the binding free-energy difference and entropy changes upon oil solvation for PAHs at oil/brine and oil/hydrate interfaces. The detailed thermodynamic analysis conducted upon the interactions between PAHs and various interfaces identifies molecular-level mechanisms responsible for wettability alterations, which could be applicable for advancing applications in optics, microfluidics, biotechnology, medicine, as well as hydrate management.

Long-Range Ionic and Short-Range Hydration Effects Govern Strongly Anisotropic Clay Nanoparticle Interactions.

The aggregation of clay particles in aqueous solution is a ubiquitous everyday process of broad environmental and technological importance. However, it is poorly understood at the all-important atomistic level since it depends on a complex and dynamic interplay of solvent-mediated electrostatic, hydrogen bonding, and dispersion interactions. With this in mind, we have performed an extensive set of classical molecular dynamics simulations (included enhanced sampling simulations) on the interactions between model kaolinite nanoparticles in pure and salty water. Our simulations reveal highly anisotropic behavior, in which the interaction between the nanoparticles varies from attractive to repulsive depending on the relative orientation of the nanoparticles. Detailed analysis reveals that at large separation (>1.5 nm), this interaction is dominated by electrostatic effects, whereas at smaller separations, the nature of the water hydration structure becomes critical. This study highlights an incredible richness in how clay nanoparticles interact, which should be accounted for in, for example, coarse-grained models of clay nanoparticle aggregation.

Anomalous transport of colloids in heterogeneous porous media: A multi-scale statistical theory.

HYPOTHESIS: Transport of suspended colloids in heterogeneous porous media is a multi-scale process that exhibits anomalous behavior and cannot be described by the Fickian dispersion theory. Although many studies have documented colloids' transport at different length scales, a theoretical basis that links pore- to core-scale observations remains lacking. It is hypothesized that a recently proposed pore-scale statistical kinetic theory is able to capture the results observed experimentally. EXPERIMENTS: We implement a multi-scale approach via conducting core-flooding experiments of colloidal particles in a sandstone sample, simulating particles flowing through a sub-volume of the rock's digital twin, and developing a core-scale statistical theory for particles' residence times via upscaling the pore-scale kinetic theory. Experimental and computational results for solute transport are used as benchmark. FINDINGS: Based on good agreement across the scales achieved in our investigation, we show that the macroscopically observed anomalous transport is particle-type dependent and stems from particles' microscopic dispersion and deposition in heterogeneous flow fields. In particular, we reveal that residence-time distributions (i.e., breakthrough curve) obey a closed-form function that encompasses particles' microscopic dynamics, which allows investigations of a whole transition from pre-asymptotic to asymptotic behavior. The physical insights attained could be useful for interpreting experimental data and designing colloidal tracers.

Surface morphology effects on clathrate hydrate wettability.

HYPOTHESIS: Clathrate hydrates preferentially form at interfaces; hence, wetting properties play an important role in their formation, growth, and agglomeration. Experimental evidence suggests that the hydrate preparation process can strongly affect contact angle measurements, leading to the different results reported in the literature. These differences hamper technological progress. We hypothesize that changes in hydrate surface morphologies are responsible for the wide variation of contact angles reported in the literature. EXPERIMENTS: Experimental testing of our hypothesis is problematic due to the preparation history of hydrates on their surface properties, and the difficulties in advanced surface characterization. Thus, we employ molecular dynamics simulations, which allow us to systematically change the interfacial features and the system composition. Implementing advanced algorithms, we quantify fundamental thermodynamic properties to validate our observations. FINDINGS: We achieve excellent agreement with experimental observations for both atomically smooth and rough hydrate surfaces. Our results suggest that contact line pinning forces, enhanced by surface heterogeneity, are accountable for altering water contact angles, thus explaining the differences among reported experimental data. Our analysis and molecular level insights help interpret adhesion force measurements and yield a better understanding of the agglomeration between hydrate particles, providing a microscopic tool for advancing flow assurance applications.

Upcoming Transformations in Integrated Energy/Chemicals Sectors: Some Challenges and Several Opportunities.

The sociopolitical events over the past few years led to transformative changes in both the energy and chemical sectors. One of the most evident consequences of these events is the significant focus on sustainability. In fact, rather than an engaging discussion within elite social circles, the search for sustainability is now one of the hard requirements investors impose on companies. The concept of sustainability itself has developed since its inception, and now it encompasses environmental as well as socioeconomic aspects. The major players in the energy and chemical sectors seem to embrace these changes and the related challenges; in most cases, tangible ambitious goals have been proposed. For example, bp aims "to become a net zero company by 2050 or sooner, and to help the world get to net zero". Although tragic events such as the war in Ukraine directly affect global supply chains, leading to some reconsiderations in medium-term industrial and political strategies, trends and public demands seem determined to pursue ambitious sustainable goals, as tangible as the European Union's "Fit for 55" climate package, approved on May 12, 2022, which effectively bans internal combustion engines for new passenger cars and light commercial vehicles from 2035. These trends will likely lead to profound changes in both the chemical and energy sectors. While some predictions may miss the target, speculating about upcoming challenges and opportunities could help us prepare for the future. This is the purpose of this brief Perspective.

Water/oil interfacial tension reduction - an interfacial entropy driven process.

The interfacial tension (IFT) of a fluid-fluid interface plays an important role in a wide range of applications and processes. When low IFT is desired, surface active compounds (e.g. surfactants) can be added to the system. Numerous attempts have been made to relate changes in IFT arising from such compounds to the specific nature of the interface. However, the IFT is controlled by an interplay of factors such as temperature and molecular structure of surface-active compounds, which make it difficult to predict IFT as those conditions change. In this study, we present the results from molecular dynamics simulations revealing the specific role surfactants play in IFT. We find that, in addition to reducing direct contact between the two fluids, surfactants serve to increase the disorder at the interface (related to interfacial entropy) and consequently reduce the water/oil IFT, especially when surfactants are present at high surface density. Our results suggest that surfactants that yield more disordered interfacial films (e.g. with flexible and/or unsaturated tails) reduce the water/oil IFT more effectively than surfactants which yield highly ordered interfacial films. Our results shed light on some of the factors that control IFT and could have important practical implications in industrial applications such as the design of cosmetics, food products, and detergents.

Effects of surface contamination on the interfacial properties of CO2/water/calcite systems.

Understanding the wetting properties of reservoir rocks can be of great benefit for advanced applications such as the effective trapping and geological storage of CO2. Despite their importance, not all mechanisms responsible for wetting mineral surfaces in subsurface environments are well understood. Factors such as temperature, pressure and salinity are often studied, achieving results with little unanimity; other possible factors are left somewhat unexplored. One such factor is the effect of contamination. In the present study, the effects of adding a non-aqueous organic contaminant, ethanol, on the CO2-water interfacial tension (IFT) and the CO2/water/calcite contact angle were investigated using molecular dynamics simulations. Within the conditions studied, relatively small amounts of ethanol cause a significant decrease in the CO2-water IFTs, as well as a pronounced increase in the water-calcite-CO2 three phase contact angle. The latter result is due to the decrease of the IFT between CO2 and water and the strong adsorption of ethanol on the solid substrate. These findings could be helpful for explaining how impurities can affect experimental data and could lead to effective carbon sequestration strategies.