TY - JOUR
T1 - Hydrogen isotope separation in metal-organic frameworks
T2 - Kinetic or chemical affinity quantum-sieving?
AU - Savchenko, Ievgeniia
AU - Mavrandonakis, Andreas
AU - Heine, Thomas
AU - Oh, Hyunchul
AU - Teufel, Julia
AU - Hirscher, Michael
N1 - Publisher Copyright:
© 2015
PY - 2015/11/1
Y1 - 2015/11/1
N2 - Recently we reported hydrogen isotope separation by quantum sieving in metal-organic framework MFU-4, a framework exhibiting gates of about the same size as the molecular radii of D2 and H2. Due to its smaller effective particle size, D2 penetrates preferentially through the framework, resulting in remarkable selectivity. Surprisingly, MFU-4l, a material of very similar composition, but with substantially larger gate openings, shows appreciable hydrogen isotopologue selectivity. This selectivity occurs at low temperature and is smaller compared to earlier reported CPO-27, a framework exhibiting open metal sites. We show that this is caused by different adsorption enthalpies which are the result of quantum effects. It turns out that two independent hydrogen isotope separation mechanisms have been reported for MOFs: while kinetic quantum sieving works at cryogenic temperatures for materials with small pores, different adsorption energies allow chemical affinity quantum sieving. This effect is maximized by strong adsorption centers, which allow high selectivity at high temperatures (100 K and above), and is more appropriate for the rational design of isotope separation membranes.
AB - Recently we reported hydrogen isotope separation by quantum sieving in metal-organic framework MFU-4, a framework exhibiting gates of about the same size as the molecular radii of D2 and H2. Due to its smaller effective particle size, D2 penetrates preferentially through the framework, resulting in remarkable selectivity. Surprisingly, MFU-4l, a material of very similar composition, but with substantially larger gate openings, shows appreciable hydrogen isotopologue selectivity. This selectivity occurs at low temperature and is smaller compared to earlier reported CPO-27, a framework exhibiting open metal sites. We show that this is caused by different adsorption enthalpies which are the result of quantum effects. It turns out that two independent hydrogen isotope separation mechanisms have been reported for MOFs: while kinetic quantum sieving works at cryogenic temperatures for materials with small pores, different adsorption energies allow chemical affinity quantum sieving. This effect is maximized by strong adsorption centers, which allow high selectivity at high temperatures (100 K and above), and is more appropriate for the rational design of isotope separation membranes.
KW - Hydrogen isotope separation
KW - Metal-organic framework
KW - Quantum sieving
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U2 - 10.1016/j.micromeso.2015.03.017
DO - 10.1016/j.micromeso.2015.03.017
M3 - Article
AN - SCOPUS:84928386939
SN - 1387-1811
VL - 216
SP - 133
EP - 137
JO - Microporous and Mesoporous Materials
JF - Microporous and Mesoporous Materials
ER -