Highly selective quantum sieving of D2 from H2 by a metal-organic framework as determined by gas manometry and infrared spectroscopy

J Am Chem Soc. 2013 Jun 26;135(25):9458-64. doi: 10.1021/ja402103u. Epub 2013 Jun 12.

Abstract

The quantum sieving effect between D2 and H2 is examined for a series of metal-organic frameworks (MOFs) over the temperature range 77-150 K. Isothermal adsorption measurements demonstrate a consistently larger isosteric heat of adsorption for D2 vs H2, with the largest difference being 1.4 kJ/mol in the case of Ni-MOF-74. This leads to a low-pressure selectivity for this material that increases from 1.5 at 150 K to 5.0 at 77 K. Idealized adsorption solution theory indicates that the selectivity decreases with increasing pressure, but remains well above unity at ambient pressure. Infrared measurements on different MOF materials show a strong correlation between selectivity and the frequency of the adsorbed H2 translational band. This confirms that the separation is predominantly due to the difference in the zero-point energies of the adsorbed isotopologues.

Publication types

  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Deuterium / chemistry*
  • Hydrogen / chemistry*
  • Organometallic Compounds / chemistry*
  • Quantum Theory*
  • Temperature

Substances

  • Organometallic Compounds
  • Hydrogen
  • Deuterium