Effects of molecular sieving and electrostatic enhancement in the adsorption of organic compounds on the zeolitic imidazolate framework ZIF-8.
In this work, the adsorption behavior of a range of organic vapors and gases on the zeolitic imidazolate framework, ZIF-8, is investigated using an inverse gas chromatography (IGC) methodology at the zero-coverage limit and elevated temperatures. The measured thermodynamic values and surface energies for the adsorption of n-alkanes on ZIF-8 are found to be reduced from those previously reported for IRMOF-1. This reduction is most likely an effect of the predominately organic accessible surface of ZIF-8 and the resulting weaker interactions in comparison to IRMOF-1. The pore aperture size of ZIF-8, which is significantly reduced from that of IRMOF-1, is seen to introduce molecular sieving effects for branched alkanes, aromatics, and heavily halogenated compounds. Deformation polarizabilities of the adsorbates were used to calculate the specific adsorption free energy, and it is determined that the specific effects account for around 1-5 kJ/mol, or between 10% and 70% of the total free energy of adsorption for the sorbates studied (at 250 °C). The importance of electrostatic forces was seen in the significantly enhanced adsorption of propylene and ethylene in comparison to their respective alkanes and in the direct correlation shown between the specific components of the free energy of adsorption and the adsorbate's dipole moment.
Luebbers
Matthew T
MT
Department of Chemical and Biomolecular Engineering, University of Illinois, Urbana, Illinois 61801, USA.
Wu
Tianjiao
T
Shen
Lingjuan
L
Masel
Richard I
RI