Diffusion of linear paraffins in nanoporous silica

The diffusion of hexane, heptane, octane, and decane in nanoporous MCM-41 silica at various temperatures is investigated by the zero-length-column method. The diffusion coefficients are derived by a complete-time-range analysis of desorption curves at different purge flow rates and temperatures. The results show that the calculated low-coverage diffusivity values decrease monotonically, and the derived Henry's law constants increase, as the carbon number of paraffins increases. The study reveals that transport is strongly influenced by intracrystalline diffusion and dominated by the sorbate-sorbent interaction. The diffusion activation energy and adsorption isosteric heat at zero loading increase monotonically with the carbon number of linear paraffins, but their ratio is essentially constant for each adsorbate compound.

Application of density functional theory to equilibrium adsorption of argon and nitrogen on amorphous silica surface

We present a new version of non-local density functional theory (NL-DFT) adapted to description of vapor adsorption isotherms on amorphous materials like non-porous silica. The novel feature of this approach is that it accounts for the roughness of adsorbent surface. The solid–fluid interaction is described in the same framework as in the case of fluid–fluid interactions, using the Weeks–Chandler–Andersen (WCA) scheme and the Carnahan–Starling (CS) equation for attractive and repulsive parts of the Helmholtz free energy, respectively. Application to nitrogen and argon adsorption isotherms on non-porous silica LiChrospher Si-1000 at their boiling points, recently published by Jaroniec and co-workers, has shown an excellent correlative ability of our approach over the complete range of pressures, which suggests that the surface roughness is mostly the reason for the observed behavior of adsorption isotherms. From the analysis of these data, we found that in the case of nitrogen adsorption short-range interactions between oxygen atoms on the silica surface and quadrupole of nitrogen molecules play an important role. The approach presented in this paper may be further used in quantitative analysis of adsorption and desorption isotherms in cylindrical pores such as MCM-41 and carbon nanotubes.

Capillary phenomena in the framework of the two-dimensional density functional theory

We present results of application of the density functional theory (DFT) to adsorption and desorption in finite and infinite cylindrical pores accounting for the density distribution in radial and axial directions. Capillary condensation via formation of bridges is considered using canonical and grand canonical versions of the 2D DFT. The potential barrier of nucleation is determined as a function of the bulk pressure and the pore diameter. In the framework of the conventional assumptions on intermolecular interactions both 1D and 2D DFT versions lead to the same results and confirm the classical scenario of condensation and evaporation: the condensation occurs at the vapor-like spinodal point, and the evaporation corresponds to the equilibrium transition pressure. The analysis of experimental data on argon and nitrogen adsorption on MCM-41 samples seems to not completely corroborate this scenario, with adsorption branch being better described by the equilibrium pressure - diameter dependence. This points to the necessity of the further development of basic representations on the hysteresis phenomena.

Modeling of adsorption and nucleation in infinite cylindrical pores by two-dimensional density functional theory

In this paper, we present an analysis of argon adsorption in cylindrical pores having amorphous silica structure by means of a nonlocal density functional theory (NLDFT). In the modeling, we account for the radial and longitudinal density distributions, which allow us to consider the interface between the liquidlike and vaporlike fluids separated by a hemispherical meniscus in the canonical ensemble. The Helmholtz free energy of the meniscus was determined as a function of pore diameter. The canonical NLDFT simulations show the details of density rearrangement at the vaporlike and liquidlike spinodal points. The limits of stability of the smallest bridge and the smallest bubble were also determined with the canonical NLDFT. The energy of nucleation as a function of the bulk pressure and the pore diameter was determined with the grand canonical NLDFT using an additional external potential field. It was shown that the experimentally observed reversibility of argon adsorption isotherms at its boiling point up to the pore diameter of 4 nm is possible if the potential barrier of 22kT is overcome due to density fluctuations.

Modeling of adsorption in finite cylindrical pores by means of density functional theory

Adsorption of argon at its boiling point infinite cylindrical pores is considered by means of the non-local density functional theory (NLDFT) with a reference to MCM-41 silica. The NLDFT was adjusted to amorphous solids, which allowed us to quantitatively describe argon adsorption isotherm on nonporous reference silica in the entire bulk pressure range. In contrast to the conventional NLDFT technique, application of the model to cylindrical pores does not show any layering before the phase transition in conformity with experimental data. The finite pore is modeled as a cylindrical cavity bounded from its mouth by an infinite flat surface perpendicular to the pore axis. The adsorption of argon in pores of 4 and 5 nm diameters is analyzed in canonical and grand canonical ensembles using a two-dimensional version of NLDFT, which accounts for the radial and longitudinal fluid density distributions. The simulation results did not show any unusual features associated with accounting for the outer surface and support the conclusions obtained from the classical analysis of capillary condensation and evaporation. That is, the spontaneous condensation occurs at the vapor-like spinodal point, which is the upper limit of mechanical stability of the liquid-like film wetting the pore wall, while the evaporation occurs via a mechanism of receding of the semispherical meniscus from the pore mouth and the complete evaporation of the core occurs at the equilibrium transition pressure. Visualization of the pore filling and empting in the form of contour lines is presented.

Postsynthesis stabilization of free-standing mesoporous silica films

Mixed ammonia-water vapor postsynthesis treatment provides a simple and convenient method for stabilizing mesostructured silica films. X-ray diffraction, transmission electron microscopy, nitrogen adsorption/desorption, and solid-state NMR (C-13, Si-29) were applied to study the effects of mixed ammonia-water vapor at 90 degreesC on the mesostructure of the films. An increased cross-linking of the silica network was observed. Subsequent calcination of the silica films was seen to cause a bimodal pore-size distribution, with an accompanying increase in the volume and surface area ratios of the primary (d = 3 nm) to secondary (d = 5-30 nm) pores. Additionally, mixed ammonia-water treatment was observed to cause a narrowing of the primary pore-size distribution. These findings have implications for thin film based applications and devices, such as sensors, membranes, or surfaces for heterogeneous catalysis.