Adsorptive Separation of Methanol–Acetone on Isostructural Series of Metal–Organic Frameworks M‑BTC (M = Ti, Fe, Cu, Co, Ru, Mo): A Computational Study of Adsorption Mechanisms and Metal-Substitution Impacts

The adsorptive separation properties of M-BTC isostructural series (M = Ti, Fe, Cu, Co, Ru, Mo) for methanol–acetone mixtures were investigated by using various computational procedures of grand canonical Monte Carlo simulations (GCMC), density functional theory (DFT), and ideal adsorbed solution theory (IAST), following with comprehensive understanding of adsorbate–metal interactions on the adsorptive separation behaviors. The obtained results showed that the single component adsorptions were driven by adsorbate–framework interactions at low pressures and by framework structures at high pressures, among which the mass effects, electrostatics, and geometric accessibility of the metal sites also played roles. In the case of methanol-acetone separation, the selectivity of methanol on M-BTCs decreased with rising pressures due to the pressure-dependent separation mechanisms: the cooperative effects between methanol and acetone hindered the separation at low pressures, whereas the competitive effects of acetone further resulted in the lower selectivity at high pressures. Among these M-BTCs, Ti and Fe analogues exhibited the highest thermodynamic methanol/acetone selectivity, making them promising for adsorptive methanol/acetone separation processes. The investigation provides mechanistic insights on how the nature of metal centers affects the adsorption properties of MOFs, and will further promote the rational design of new MOF materials for effective gas mixture separation