Heterogeneous Microscopic Dynamics of Intruded Water in a Superhydrophobic Nanoconfinement: Neutron Scattering and Molecular Modeling.

With their strong confining porosity and versatile surface chemistry, zeolitic imidazolate frameworks-including the prototypical ZIF-8-display exceptional properties for various applications. In particular, the forced intrusion of water at high pressure (∼25 MPa) into ZIF-8 nanopores is of interest for energy storage. Such a system reveals also ideal to study experimentally water dynamics and thermodynamics in an ultrahydrophobic confinement. Here, we report on neutron scattering experiments to probe the molecular dynamics of water within ZIF-8 nanopores under high pressure up to 38 MPa. In addition to an overall confinement-induced slowing down, we provide evidence for strong dynamical heterogeneities with different underlying molecular dynamics. Using complementary molecular simulations, these heterogeneities are found to correspond to different microscopic mechanisms inherent to vicinal molecules located in strongly adsorbing sites (ligands) and other molecules nanoconfined in the cavity center. These findings unveil a complex microscopic dynamics, which results from the combination of surface residence times and exchanges between the cavity surface and center.

Convective drying of a porous medium with a paste cover.

The convective drying of a composite system made of a porous medium covered with a paste is a situation often encountered with soils, roads, building and cultural heritage materials. Here we discuss the basic mechanisms at work during the drying of a model composite system made of a homogeneous paste covering a simple granular packing. We start by reviewing the rather well-known case of the convective drying of a simple granular packing (i.e. without paste cover), which serves as a reference for physical interpretations. We show that a simple model assuming homogeneous desaturation followed by a progressive development of a dry front from the sample free surface is in agreement with observations of the internal liquid distribution variations in time. In particular, this model is able to reproduce the saturation vs. time curves of various simple granular systems, which supports our understanding of physical mechanisms at work. Then we show the detailed characteristics of drying of initially saturated model composite systems (with kaolin or cellulose paste) with the help of MRI measurements providing the liquid distribution in the sample at different times during the process up to the very last stages of drying. It appears that the granular medium is unaffected (i.e. remains saturated) during an initial period during which the paste shrinks and finally forms a sufficiently rigid porous structure which will not any more shrink later on. Then the drying process is governed by capillary effects down to very low saturation. Over a wide range of saturations both media desaturate homogeneously (within each medium) at different rates which depend on the specific porous structure of the media, so as to maintain capillary equilibrium throughout the sample. During these different stages the drying rate of the whole system remains constant. For sufficiently low saturation in the paste a dry front can develop, both in the paste and the porous medium below, and the drying rate now decreases. These results show that in a drying composite system liquid extraction can occur more or less simultaneously in the different parts of the material up to the very last stages of drying. The corresponding evolution of the distributions of liquid in the different parts of the sample also provides key information for the prediction of ion or particle transport and accumulation in the different parts of a composite system.

Electrostatic interactions between ions near Thomas-Fermi substrates and the surface energy of ionic crystals at imperfect metals.

The electrostatic interaction between two charged particles is strongly modified in the vicinity of a metal. This situation is usually accounted for by the celebrated image charges approach, which was further extended to account for the electronic screening properties of the metal at the level of the Thomas-Fermi description. In this paper we build upon a previous approach [M. A. Vorotyntsev and A. A. Kornyshev, Zh. Eksp. Teor. Fiz., 1980, 78(3), 1008-1019] and successive works to calculate the 1-body and 2-body electrostatic energy of ions near a metal in terms of the Thomas-Fermi screening length. We propose workable approximations suitable for molecular simulations of ionic systems close to metallic walls. Furthermore, we use this framework to calculate analytically the electrostatic contribution to the surface energy of a one dimensional crystal at a metallic wall and its dependence on the Thomas-Fermi screening length. These calculations provide a simple interpretation for the surface energy in terms of image charges, which allows for an estimation of the interfacial properties in more complex situations of a disordered ionic liquid close to a metal surface. The counter-intuitive outcome is that electronic screening, as characterized by a molecular Thomas-Fermi length lTF, profoundly affects the wetting of ionic systems close to a metal, in line with the recent experimental observation of capillary freezing of ionic liquids in metallic confinement.

Freezing of water confined at the nanoscale.

Freezing of water in hydrophilic nanopores (D=1.2 nm) is probed at the microscopic scale using x-ray diffraction, Raman spectroscopy, and molecular simulation. A freezing scenario, which has not been observed previously, is reported; while the pore surface induces orientational order of water in contact with it, water does not crystallize at temperatures as low as 173 K. Crystallization at the surface is suppressed as the number of hydrogen bonds formed is insufficient (even when including hydrogen bonds with the surface), while crystallization in the pore center is hindered as the curvature prevents the formation of a network of tetrahedrally coordinated molecules. This sheds light on the concept of an ubiquitous unfreezable water layer by showing that the latter has a rigid (i.e., glassy) liquidlike structure, but can exhibit orientational order.

Thermodynamics of water confined in porous calcium-silicate-hydrates.

Water within pores of cementitious materials plays a crucial role in the damage processes of cement pastes, particularly in the binding material comprising calcium-silicate-hydrates (C-S-H). Here, we employed Grand Canonical Monte Carlo simulations to investigate the properties of water confined at ambient temperature within and between C-S-H nanoparticles or "grains" as a function of the relative humidity (%RH). We address the effect of water on the cohesion of cement pastes by computing fluid internal pressures within and between grains as a function of %RH and intergranular separation distance, from 1 to 10 Å. We found that, within a C-S-H grain and between C-S-H grains, pores are completely filled with water for %RH larger than 20%. While the cohesion of the cement paste is mainly driven by the calcium ions in the C-S-H, water facilitates a disjoining behavior inside a C-S-H grain. Between C-S-H grains, confined water diminishes or enhances the cohesion of the material depending on the intergranular distance. At very low %RH, the loss of water increases the cohesion within a C-S-H grain and reduces the cohesion between C-S-H grains. These findings provide insights into the behavior of C-S-H in dry or high-temperature environments, with a loss of cohesion between C-S-H grains due to the loss of water content. Such quantification provides the necessary baseline to understand cement paste damaging upon extreme thermal, mechanical, and salt-rich environments.

Molecular simulation of nitrogen adsorption in nanoporous silica.

This article reports on a molecular simulation study of nitrogen adsorption and condensation at 77 K in atomistic silica cylindrical nanopores (MCM-41). Two models are considered for the nitrogen molecule and its interaction with the silica substrate. In the "pea" model, the nitrogen molecule is described as a single Lennard-Jones sphere and only Lennard-Jones interactions between the nitrogen molecule and the oxygens atoms of the silica substrate are taken into account. In the "bean" model (TraPPE force field), the nitrogen molecule is composed of two Lennard-Jones sites and a linear array of three charges on the atomic positions and at the center of the nitrogen-nitrogen bond. In the bean model, the interactions between the sites on the nitrogen molecule and the Si, O, and H atoms of the substrate are the sum of the Coulombic and dispersion interactions with a repulsive short-range contribution. The data obtained with the pea and bean models in silica nanopores conform to the typical behavior observed in the experiments for adsorption/condensation in cylindrical MCM-41 nanopores; the adsorbed amount increases continuously in the multilayer adsorption regime until an irreversible jump occurs because of capillary condensation and evaporation of the fluid within the pore. Our results suggest that the pea model can be used for characterization purposes where one is interested in capturing the global experimental behavior upon adsorption and desorption in silica nanopores. However, the bean model is more suitable to investigating the details of the interaction with the surface because this model, which accounts for the partial charges located on the nitrogen atoms of the molecule (quadrupole), allows a description of the specific interactions between this adsorbate and silica surfaces (silanol groups and siloxane bridges) or grafted silica surfaces. In particular, the bean model provides a more realistic picture of nitrogen adsorption in the vicinity of silica surfaces or confined in silica nanopores, where the isosteric heat of adsorption curves show that the nitrogen molecule in this model is sensitive to the surface heterogeneity.

Molecular simulation of water confined in nanoporous silica.

This paper reports on a molecular simulation study of the thermodynamics, structure and dynamics of water confined at ambient temperature in hydroxylated silica nanopores of a width H = 10 and 20 Å. The adsorption isotherms for water in these nanopores resemble those observed for experimental samples; the adsorbed amount increases continuously in the multilayer adsorption regime until a jump occurs due to capillary condensation of the fluid within the pore. Strong layering of water in the vicinity of the silica surfaces is observed as marked density oscillations are observed up to 8 Å from the surface in the density profiles for confined water. Our results indicate that water molecules within the first adsorbed layer tend to adopt a H-down orientation with respect to the silica substrate. For all pore sizes and adsorbed amounts, the self-diffusivity of confined water is lower than the bulk, due to the hydrophilic interaction between the water molecules and the hydroxylated silica surface. Our results also suggest that the self-diffusivity of confined water is sensitive to the adsorbed amount.

Melting mechanism of monolayers adsorbed in cylindrical pores: the influence of the pore wall roughness.

We have analyzed the mechanism of melting of molecular layers adsorbed in porous materials with cylindrical pores and rough pore walls. The working example studied here is a monolayer of methane molecules adsorbed in MCM-41 pore of diameter 2R=4 nm. Both experimental (neutron scattering) and simulation (Monte Carlo) results demonstrate the strong influence of the wall roughness on the melting mechanism. In particular, the transformation between solidlike and liquidlike monolayer phases adsorbed on a rough surface is observed over a broad temperature range, and solidlike properties persist even above the bulk methane melting temperature.

Freezing of fluids confined in a disordered nanoporous structure.

Freezing of a simple fluid in a disordered nanoporous carbon is studied using molecular simulations. Only partial crystallization occurs, and the confined phase is composed of crystalline and amorphous nanodomains. This freezing behavior departs strongly from that for nanopores of simple geometry. We present a method for analyzing the freezing in such disordered materials in terms of a transition in the average size and number of crystalline clusters. The results provide a basis for the interpretation of experiments on freezing in such materials, particularly 1H-NMR and scattering experiments.

Effects of confinement on freezing and melting.

We present a review of experimental, theoretical, and molecular simulation studies of confinement effects on freezing and melting. We consider both simple and more complex adsorbates that are confined in various environments (slit or cylindrical pores and also disordered porous materials). The most commonly used molecular simulation, theoretical and experimental methods are first presented. We also provide a brief description of the most widely used porous materials. The current state of knowledge on the effects of confinement on structure and freezing temperature, and the appearance of new surface-driven and confinement-driven phases are then discussed. We also address how confinement affects the glass transition.

A grand canonical Monte Carlo study of capillary condensation in mesoporous media: effect of the pore morphology and topology.

We study by means of Grand Canonical Monte Carlo simulations the condensation and evaporation of argon at 77 K in nanoporous silica media of different morphology or topology. For each porous material, our results are compared with data obtained for regular cylindrical pores. We show that both the filling and emptying mechanisms are significantly affected by the presence of a constriction. The simulation data for a constricted pore closed at one end reproduces the asymmetrical shape of the hysteresis loop that is observed for many real disordered porous materials. The adsorption process is a quasicontinuous mechanism that corresponds to the filling of the different parts of the porous material, cavity, and constriction. In contrast, the desorption branch for this pore closed at one end is brutal because the evaporation of Ar atoms confined in the largest cavity is triggered by the evaporation of the fluid confined in the constriction (which isolates the cavity from the gas reservoir). This evaporation process conforms to the classical picture of "pore blocking effect" proposed by Everett many years ago. We also simulate Ar adsorption in a disordered porous medium, which mimics a Vycor mesoporous silica glass. The adsorption isotherm for this disordered porous material having both topological and morphological defects presents the same features as that for the constricted pore (quasicontinuous adsorption and steep desorption process). However, the larger degree of disorder of the Vycor surface enhances these main characteristics. Finally, we show that the effect of the disorder, topological and/or morphological, leads to a significant lowering of the capillary condensation pressure compared to that for regular cylindrical nanopores. Also, our results suggest that confined fluids isolated from the bulk reservoir evaporate at a pressure driven by the smallest size of the pore.

Grand canonical Monte Carlo simulation of argon adsorption at the surface of silica nanopores: effect of pore size, pore morphology, and surface roughness.

Argon adsorption (77 K) in atomistic silica nanopores of various sizes and shapes has been studied by means of grand canonical Monte Carlo simulations (GCMC). We discuss the effects of confinement (pore size), pore morphology (ellipsoidal, hexagonal, constricted pore), and surface texture (rough/smooth) on the thickness variation of the adsorbed film with pressure onto the disordered inner surface of porous materials (usually called t-plot or t-curve). We show that no confinement effect occurs when the diameter of the regular cylindrical pore is larger than 10 nm. For pores smaller than 6 nm, we find that the film thickness increases as the pore size decreases. We show that the adsorption isotherm in the rough pore can be described as the sum of an adsorbed amount similar to that found for a smooth pore (of the same radius) and a constant contribution due to atoms "trapped" in the infractuosities of the rough surface which act as a microporous texture. Simulation snapshots for Ar adsorption in hexagonal and ellipsoidal smooth pores indicate that at low pressures the gas/adsorbate interface retains memory of the pore shape and becomes cylindrical prior to the capillary condensation of the fluid in the pore. The film thickness in the hexagonal pore is close to that obtained for a cylindrical pore having a similar dimension. By contrast, we find that the film thickness for an ellipsoidal pore is always larger than that for an equivalent cylindrical pore (having the same length and volume but a circular section). We show that this effect strengthens as the pore size decreases and/or the pore asymmetry increases. Ar adsorption in a cylindrical constricted pore shows that the presence of the narrower part considerably modifies the adsorption mechanism. Finally, we report GCMC simulations of Ar adsorption (77 K) on a plane silica reference substrate for different intermolecular potentials. We discuss the effect of the interaction on the shape of the adsorption isotherm and compare our results with experiments.

Adsorption in noninterconnected pores open at one or at both ends: a reconsideration of the origin of the hysteresis phenomenon.

We report on an experimental study of adsorption isotherm of nitrogen onto porous silicon with noninterconnected pores open at one or at both ends in order to check for the first time the old (1938) but always current idea based on Cohan's description which suggests that the adsorption of gas should occur reversibly in the first case and irreversibly in the second one. Hysteresis loops, the shape of which is usually associated with interconnections in porous media, are observed whether the pores are open at one or at both ends, in contradiction with Cohan's model.