Carbon molecular sieves: Reconstruction of atomistic structural models with experimental constraints

We propose a novel methodology for developing experimentally informed structural models of disordered carbon molecular sieves. The hybrid reverse Monte Carlo simulation method coupled with wide-angle X-ray scattering experiments is used for constructing an atomistic level model of a representative sample of carbon molecular sieve film (CMS-F) synthesized in our laboratory. We found that CMS-F possesses a disordered matrix enriched with bended carbon chains and various carbon clusters as opposed to the turbostratic carbon or graphite-like microcrystals. The pore structure of CMS-F has a defected lamellar morphology of one-dimensional periodicity with narrow (∼0.4 nm) micropores. The model is applied to study adsorption properties of CMS-F with respect to adsorbates of practical interest, such as N₂, H₂, CO, and C₆H₆. Special attention is paid to the phase transformations in the course of adsorption. In particular, we show theoretically and confirm experimentally that nitrogen solidifies within CMS-F pores at 77 K upon adsorption of 5 mmol/g, and its further adsorption is associated with the adsorbed phase compression induced by strong surface forces.