Monte-Carlo Multiscale Simulation Study of Argon Adsorption/Desorption Hysteresis in Mesoporous Heterogeneous Tubular Pores like MCM-41 or Oxidized Porous Silicon

摘要

In a recent paper [J. Chem. Phys. 2007,127,154701] a multiscale approach was introduced which allowed calculation of adsorption/desorption hysteresis for fluid confined in a single mesoporous, heterogeneous tubular pore. The main interest in using such an approach is that it allows one to reconcile a molecular simulation approach generally limited to the nanometer scale (atomistic description of the confined fluid and pore roughness) with the much larger scale (micrometer) relevant to understand the complexity of adsorption/desorption hysteresis (the numerous metastable states in the hysteresis loop are a consequence of the large-scale disorder in the porous material). In this paper, this multiscale approach is used to study adsorption phenomena in mesoporous models made of a collection of disordered, noninterconnected tubular pores, as MCM-41 or porous silicon. A double distribution is introduced: one to characterize the disorder in a given pore, and the other to characterize the disorder between the pores. We consider two distribution shapes: Gaussian and uniform truncated and two cases of pores open at one or both ends. These models are expected to cover a wide variety of real materials made of independent pores, as MCM-41 and oxidized porous silicon. A large variety of hysteresis shapes is obtained, ranging from almost parallel adsorption/desorption branches typical of MCM-41 adsorption to triangular hysteresis typical of porous silicon. The structure of the metastable states inside the hysteresis (scanning adsorption/desorption curves) is also examined. The results are expected to be useful to experimentalists who want to infer pore structure and level of disorder from experimental adsorption/desorption experiments.