New Microporous Materials for Acetylene Storage and C2H2/CO2 Separation: Insights from Molecular Simulations

Force-field based grand-canonical Monte Carlo simulations are used to investigate the acetylene and carbon dioxide uptake capacity, as well as the C2H2/CO2 adsorption selectivity of three novel microporous materials: Magnesium formate, Cu-3(btc)(2), and cucurbit[6]uril. Because no comparable computational studies of acetylene adsorption have been reported so far, the study focuses on systems for which experimental data are available to permit a thorough validation of the simulation results. The results for magnesium formate are in excellent agreement with experiment. The simulation predicts a high selectivity for acetylene over CO2, which can be understood from a detailed analysis of the structural features that determine the affinity of Mg-formate towards C2H2. For Cu-3(btc)(2), preliminary calculations reveal the necessity to include the interaction of the sorbate molecules with the unsaturated metal sites, which is done by means of a parameter adjustment based on ab-initio calculations. In spite of the high C2H2 storage capacity, the C2H2/CO2 selectivity of this material is very modest. The simulation results for the porous organic crystal cucurbit[E]uril show that the adsorption characteristics that have been observed experimentally, particularly the very high isosteric heat of adsorption, cannot be understood when an ideal structure is assumed. It is postulated that structural imperfections play a key role in determining the C2H2 adsorption behavior of this material, and this proposition is supported by additional calculations.