Adsorption Properties of MFM-400 and MFM-401 with CO2 and Hydrocarbons: Selectivity Derived from Directed Supramolecular Interactions
Por:
Ibarra, Ilich A., Mace, Amber, Yang, Sihai, Sun, Junliang, Lee, Sukyung, Chang, Jong-San, Laaksonen, Aatto, Schroeder, Martin, Zou, Xiaodong
Publicada:
1 ago 2016
Resumen:
([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.
Filiaciones:
Ibarra, Ilich A.:
Stockholm Univ, Berzelii Ctr EXSELENT Porous Mat, SE-10691 Stockholm, Sweden
Stockholm Univ, Dept Mat & Environm Chem, SE-10691 Stockholm, Sweden
Univ Nacl Autonoma Mexico, Inst Invest Mat, Circuito Exterior S-N, Mexico City 04510, DF, Mexico
Mace, Amber:
Stockholm Univ, Berzelii Ctr EXSELENT Porous Mat, SE-10691 Stockholm, Sweden
Stockholm Univ, Dept Mat & Environm Chem, SE-10691 Stockholm, Sweden
Yang, Sihai:
Univ Nottingham, Sch Chem, Nottingham NG7 2RD, England
Univ Manchester, Sch Chem, Manchester M13 9PL, Lancs, England
Sun, Junliang:
Stockholm Univ, Berzelii Ctr EXSELENT Porous Mat, SE-10691 Stockholm, Sweden
Stockholm Univ, Dept Mat & Environm Chem, SE-10691 Stockholm, Sweden
Lee, Sukyung:
Korea Res Inst Chem Technol, Catalysis Ctr Mol Engn, POB 107, Yuseong 305600, Daejon, South Korea
Chang, Jong-San:
Korea Res Inst Chem Technol, Catalysis Ctr Mol Engn, POB 107, Yuseong 305600, Daejon, South Korea
Sungkyunkwan Univ, Dept Chem, Suwon 440476, South Korea
Laaksonen, Aatto:
Stockholm Univ, Berzelii Ctr EXSELENT Porous Mat, SE-10691 Stockholm, Sweden
Stockholm Univ, Dept Mat & Environm Chem, SE-10691 Stockholm, Sweden
Schroeder, Martin:
Univ Nottingham, Sch Chem, Nottingham NG7 2RD, England
Univ Manchester, Sch Chem, Manchester M13 9PL, Lancs, England
Zou, Xiaodong:
Stockholm Univ, Berzelii Ctr EXSELENT Porous Mat, SE-10691 Stockholm, Sweden
Stockholm Univ, Dept Mat & Environm Chem, SE-10691 Stockholm, Sweden
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