Fluids confined in nanopores exhibit properties different from the properties of the same fluids in bulk; among these properties is the isothermal compressibility or elastic modulus. The modulus of a fluid in nanopores can be extracted from ultrasonic experiments or calculated from molecular simulations. Using Monte Carlo simulations in the grand canonical ensemble, we calculated the modulus for liquid argon at its normal boiling point (87.3 K) adsorbed in model silica pores of two different morphologies and various sizes. For spherical pores, for all the pore sizes (diameters) exceeding 2 nm, we obtained a logarithmic dependence of fluid modulus on the vapor pressure. Calculation of the modulus at saturation showed that the modulus of the fluid in spherical pores is a linear function of the reciprocal pore size. The calculation of the modulus of the fluid in cylindrical pores appeared too scattered to make quantitative conclusions. We performed additional simulations at higher temperature (119.6 K), at which Monte Carlo insertions and removals become more efficient. The results of the simulations at higher temperature confirmed both regularities for cylindrical pores and showed quantitative difference between the fluid moduli in pores of different geometries. Both of the observed regularities for the modulus stem from the Tait-Murnaghan equation applied to the confined fluid. Our results, along with the development of the effective medium theories for nanoporous media, set the groundwork for analysis of the experimentally measured elastic properties of fluid-saturated nanoporous materials.
Nitrogen adsorption is one of the main characterization techniques for nanoporous materials. The experimental adsorption isotherm provides information about the surface area and pore size distribution (PSD) for a sample. In this work we show that additional insight into PSD can be gained when the speed of sound propagation through a sample is measured during nitrogen adsorption experiment. We analyzed published experimental data on ultrasound propagation through a nanoporous Vycor glass sample during nitrogen adsorption experiment. Next, we calculated the change of the longitudinal and shear moduli of the sample as a function of relative vapor pressure. From this, we show that the shear modulus of the sample does not change upon filling the pores, evidencing that adsorbed nitrogen at 77 K has zero shear modulus, similarly to a bulk liquid. The longitudinal modulus of the sample behaves differently: it changes abruptly at the capillary condensation and keeps gradually increasing thereafter. We performed Monte Carlo molecular simulations to predict the compressibility of adsorbed nitrogen and then calculated the longitudinal modulus of the nitrogen-saturated Vycor using the Gassmann equation. Our theoretical predictions nicely matched the longitudinal modulus derived from the experimental data. Additionally, we performed molecular simulations to model nitrogen adsorbed in silica pores of sizes ranging from 2 to 8 nm. We found that the isothermal elastic modulus of adsorbed nitrogen depends linearly on the inverse pore size. This dependence, along with the proposed recipe for probing the modulus of adsorbed nitrogen, sets up the grounds for extracting additional information about the porous samples, when the nitrogen adsorption is combined with ultrasonic experiments.
Silica colloidal crystals are face-centered cubic structures comprised of silica spheres with the diameters ranging between tens and hundreds of nanometers. The voids between the spheres form pores, which can be probed by nitrogen adsorption porosimetry. Here, we prepared two mesoporous samples and a macroporous reference sample and then measured nitrogen adsorption and desorption isotherms for further characterization. We proposed a straightforward procedure for calculation of the pore-size distribution of silica colloidal crystals from nitrogen adsorption isotherms. The procedure is based on the adsorption integral equation solution with a kernel of theoretical isotherms, consistent with the procedure used for many other porous materials. The solution is carried out using the nonnegative least squares (NNLS) regression with Tikhonov regularization. The kernel of mesoporous isotherms is built on the basis of the macroscopic Derjaguin−Broekhoff− de Boer (DBdB) theory of capillary condensation considering the voids as a network of spheres. Application of our procedure for the analysis of the adsorption branches of experimental isotherms resulted in bimodal distributions, where the modes matched well with the sizes of the voids in the colloidal crystals face centered cubic structure: the main mode corresponds to the octahedral voids and the second mode to the tetrahedral voids. Furthermore, we modified the surface of the samples with organics and repeated the characterization procedure for the modified samples. The resulting pore-size distribution for the samples with the modified surface matched the original one quite closely. It demonstrates the procedure as a simple and efficient technique to estimate the pore-size distribution and justifies the spherical shape approximation for the voids in the silica colloidal crystals.
Fluids adsorbing in nanoporous solids cause high solvation pressures that deform the solids and affect properties of the fluids themselves. We calculate solvation pressure of nitrogen adsorbed at 77.4 K in spherical silica mesopores using two methods: the macroscopic Derjaguin-Broekhoff-de Boer theory and molecular simulations. We show that both approaches give consistent results, and the observed pressures increase in smaller pores reaching the order of a hundred megapascals. The results are also typical for the solvation pressure in mesoporous materials, yet noticeably differ from the results for the cylindrical pore geometry. Furthermore, we show that the dependence of the solvation pressure at saturation on the reciprocal pore size is linear, and we use this relation for the calculation of the solid-liquid surface energy. The results can be employed for the prediction of the solvation pressure and the adsorption-induced deformation in the material with the spherical pore geometry.
We found a mistake in our recent work. The mistake was made in the chemical potential at saturation calculation μ 0 *: we reported μ 0 * = −9.596, while the correct value should be −9.332. Therefore, Figures 1−4 and 6 should be replotted, and although the new ones have a similar trend, they have different numerical values. Our conclusions also remain the same. The black dashed vertical lines represent the values corresponding the old saturation chemical potential value. Table 2 is also revised.Langmuir pubs.acs.org/Langmuir Addition/Correction https://dx.
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