Cristina Gavazzoni

Wetting phenomena are relevant in several technological applications, particularly those involving hydrophobic or hydrophilic surfaces. Many substrates support multiple wetting states depending on surface conditions or droplet history —a behavior known as metastability. This feature is crucial both for its theoretical complexity and for its relevance in practical applications that rely on controlling metastable states. While several experimental and computational techniques have been developed to study metastability, they tend to be complex or computationally expensive. In this work, we introduce an alternative approach based on concepts from active matter physics. We investigate the wetting behavior of a droplet placed on a pillared surface using a 3-state Cellular Potts model with a polarity term that mimics a self-propelled droplet. Applying this model to a pillared substrate with known metastable wetting states, we demonstrate that increasing activity enables the droplet to traverse free energy barriers, explore consecutive metastable states, and eventually suppress metastability entirely. Our results show that activity reduces the disparity between dry and wet states and provides a reliable framework for identifying and quantifying metastability through contact angle measurements.

Oil has become a prevalent global pollutant, stimulating the research to improve the techniques to separate oil from water. Materials with special wetting properties—primarily those that repel water while attracting oil—have been proposed as suitable candidates for this task. However, one limitation in developing efficient substrates is the limited available volume for oil absorption. In this study, we investigate the efficacy of disordered fractal materials in addressing this challenge, leveraging their unique wetting properties. Using a combination of a continuous model and Monte Carlo simulations, we characterize the hydrophobicity and oleophilicity of substrates created through ballistic deposition (BD). Our results demonstrate that these materials exhibit high contact angles for water, confirming their hydrophobic nature while allowing significant oil penetration, indicative of oleophilic behavior. The available free volume within the substrates varies from 60% to 90% of the total volume of the substrate depending on some parameters of the BD. By combining their water and oil wetting properties with a high availability of volume, the fractal substrates analyzed in this work achieve an efficiency in separating oil from water of nearly 98%, which is significantly higher compared to micro-pillared surfaces made from the same material but lacking a fractal design.

The relation between wetting properties and geometric parameters of fractal surfaces are widely discussed on the literature and, however, there are still divergences on this topic. Here we propose a simple theoretical model to describe the wetting properties of a droplet of water placed on a hierarchical structured surface and test the predictions of the model and the dependence of the droplet wetting state on the initial conditions using simulation of the 3-spin Potts model. We show that increasing the auto-similarity level of the hierarchy – called n – does not affect considerably the stable wetting state of the droplet but increases its contact angle. Simulations also explicit the existence of metastable states on this type of surfaces and shows that, when n increases, the metastability becomes more pronounced. Finally we show that the fractal dimension of the surface is not a good predictor of the contact angle of the droplet.

Several oil–water separation techniques have been proposed to improve the capacity of cleaning water. With the technological possibility of producing materials with antagonist wetting behavior, for example, a substrate that repels water and absorbs oil, the understanding of the properties that control this selective capacity has increased with the goal of being used as the mechanism to separate mixed liquids. Besides the experimental advance in this field, less is known from the theoretical side. In this work, we propose a theoretical model to predict the wetting properties of a given substrate and introduce simulations with a four-spin cellular Potts model to study its efficiency in separating water from oil. Our results show that the efficiency of the substrates depends both on the interaction between the liquids and on the wetting behavior of the substrates itself. The water behavior of the droplet composed of both liquids is roughly controlled by the hydrophobicity of the substrate. Predicting the oil behavior, however, is more complex because the substrate being oleophilic does not guarantee that the total amount of oil present on the droplet will be absorbed by the substrate. For both types of substrates considered in this work, pillared and porous with a reservoir, there is always an amount of reminiscent oil on the droplet, which is not absorbed by the substrate due to the interaction with the water and the gas. Both theoretical and numerical models can be easily modified to analyze other types of substrates and liquids.

Metal–organic frameworks (MOFs) comprise a class of highly porous nanomaterials formed by the assembly of organic molecular templates connected by metal ions. These materials exhibit a large diversity of pore size and geometry, topology, surface area, and chemical functionality. MOFs are particularly promising materials for developing new technologies for capture and storage of greenhouse gases such as methane and carbon dioxide. Here we apply the three dimensional reference interaction site model (3D-RISM) molecular theory of solvation to study the interactions of CO₂ and CH₄ with the metal–organic material MIL-47. The 3D-RISM integral equations were solved to determine the three dimensional density correlation functions of the gas (solvent) relative to the atomic positions of the MIL-47 framework, treated as static solute sites. The computed solvent spatial distributions inside MIL-47 pores were used to identify whether or not there exist preferable binding sites and the binding free energy landscape for the gas of interest at low computational costs compared with other molecular modeling techniques, such as grand canonical Monte Carlo and molecular dynamics simulations. The 3D-RISM formalism was applied to pure CO₂, pure CH₄, and binary mixtures of these gases of various compositions under different pressure conditions. The results indicate that both gases bind very weakly to MIL-47 and that this material exhibits nearly vanishing CO₂/CH₄ selectivity. The 3D-RISM computations presented here can be extended to investigate the physical adsorption of gases on other MOFs and nanoporous materials, providing an alternative low-cost computational approach to study gas capture and storage in nanoporous materials in general and, in particular, to determine the binding free-energy landscape in these systems.

We performed molecular dynamics simulations of water confined within AlPO₄-54 nanotubes. AlPO₄-54 is an artificial material made of AlO₄ and of PO₄ in tetrahedra arranged in a periodic structure forming pores of approximately 1.3 nm in diameter. This makes AlPO₄-54 an excellent candidate for practical applications, such as for water filtration and desalination. In this work, the structural and dynamical properties of the confined water are analyzed for various temperatures and water loadings. We find that the water structure is controlled by the heterogeneity of the nanopore surface with the water molecules located preferentially next to the surface of oxygens of AlPO₄-54; consequently, at very low densities, water forms helicoidal structures in string-like arrangements.