Adsorption Properties of MFM-400 and MFM-401 with CO2 and Hydrocarbons: Selectivity Derived from Directed Supramolecular Interactions

([Sc-2(OH)(2)(BPTC)]) (H4BPTC = biphenyl-3,3',5,5'-tetracarboxylit acid), MFM-400 (MFM = Manchester Framework Material; previously designated NOTT), and ([Sc(OH)-(TDA)]) (H(2)TDA = thiophene-2,5-dicarboxylic acid), MFM-401, both show xelective and, reversible capture of CO2. In particular, MFM-400 exhibits a reasonably high CO2 uptake at low pressures and competitive CO2/N-2 selectivity coupled to a moderate isosteric heat of adsorption (Q(st)) for CO2 (29.5 kJ mol(-1)) at zero coverage, thus affording a facile uptake release process. Grand canonical Monte Carlo (GCMC) and density functional theory (DFT) computational analyses of CO2 uptake in both materials confirmed preferential adsorption sites consistent with the higher CO2 uptake observed experimentally for MFM-400 over MFM-401 at low pressures. For MFM-400, the Sc-OH group participates in moderate interactions with CO2 (Q(st) = 33.5 kJ mol(-1)), and these are complemented by weak hydrogen-bonding interactions (O center dot center dot center dot H-C = 3.10-3.22 angstrom) from four surrounding aromatic -CH groups. In the case of MFM-401, adsorption is provided by cooperative interactions of CO2 with the Sc-OH group and one C-H group. The binding energies obtained by DFT analysis for the adsorption sites for both materials correlate well with the observed moderate isosteric heats of adsorption for CO2. GCMC simulations for both materials confirmed higher uptake of EtOH compared with nonpolar vapors of toluene and. cydohexane. This is in good Correlation with the experimental data, and DFT analysis confirmed the formation of a strong hydrogen bond between EtOH and the hydrogen atom of the hydroxyl group of the MFM-400 and MFM-401 framework (FIAT) with H-O-EtOH center dot center dot center dot H-O-FW distances of 1.77 arid 1.75 angstrom, respectively. In addition, the accessible regeneration of MFM-400 and MFM-401 and release of CO2 potentially provide minimal economic and environmental penalties.