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.