Molecular Determinants of Solvent Nanoseparation by Nanoporous Carbon Materials

The manifold tunable properties of nanoporous carbon materials, including high surface area, stability, conductivity, rich surface chemistry, and biocompatibility, render them a perfect platform for energy applications, catalysis, nanoseparation, and drug delivery. Here, we construct models of nanoporous carbon materials and unveil the molecular determinants of solvent nanoseparation and diffusion using coarse-grained molecular dynamics. The best nanoseparation is achieved with pore diameters just above size exclusion, and surface oxidation is the major selective modifier of diffusion of polar molecules in solvent mixtures. The shape of the solvents and, less significantly, the geometry of the pore network also influence nanoseparation. The derived Markov state model estimates the probability of a molecule following a certain path in the material. Our framework for material construction, simulation, and analysis provides a robust foundation for future investigations on how nanoseparation in nanoporous materials is governed by the interplay of surface chemistry, pore geometry, and molecular properties.