title: Capture of heavy hydrogen isotopes in a metal-organic framework with active Cu(I) sites.
abstract: The production of pure deuterium and the removal of tritium from nuclear waste are the key challenges in separation of light isotopes. Presently, the technological methods are extremely energy- and cost-intensive. Here we report the capture of heavy hydrogen isotopes from hydrogen gas by selective adsorption at Cu(I) sites in a metal-organic framework. At the strongly binding Cu(I) sites (32 kJ mol-1) nuclear quantum effects result in higher adsorption enthalpies of heavier isotopes. The capture mechanism takes place most efficiently at temperatures above 80 K, when an isotope exchange allows the preferential adsorption of heavy isotopologues from the gas phase. Large difference in adsorption enthalpy of 2.5 kJ mol-1between D2and H2results in D2-over-H2selectivity of 11 at 100 K, to the best of our knowledge the largest value known to date. Combination of thermal desorption spectroscopy, Raman measurements, inelastic neutron scattering and first principles calculations for H2/D2mixtures allows the prediction of selectivities for tritium-containing isotopologues.
authors.affiliation: Max Planck Institute for Intelligent Systems, Heisenbergstr. 3, 70569 Stuttgart, Germany.
authors.forename: I
authors.initials: I
authors.lastname: Weinrauch
authors.affiliation: Jacobs University, School of Engineering and Science, Campus Ring 1, 28759 Bremen, Germany.
authors.forename: I
authors.initials: I
authors.lastname: Savchenko
authors.affiliation: Augsburg University, Institute of Physics, Universitätsstr. 1, 86159 Augsburg, Germany.
authors.forename: D
authors.initials: D
authors.lastname: Denysenko
authors.affiliation: Max Planck Institute for Solid State Research, Heisenbergstr. 1, 70569 Stuttgart, Germany.
authors.forename: S M
authors.initials: SM
authors.lastname: Souliou
authors.affiliation: Max Planck Institute for Solid State Research, Heisenbergstr. 1, 70569 Stuttgart, Germany.
authors.forename: H-H
authors.initials: HH
authors.lastname: Kim
authors.affiliation: Max Planck Institute for Solid State Research, Heisenbergstr. 1, 70569 Stuttgart, Germany.
authors.forename: M
authors.initials: M
authors.lastname: Le Tacon
authors.affiliation: Oak Ridge National Laboratory, Spallation Neutron Source, PO Box 2008, MS6475, Oak Ridge, TN 37831-6471, USA.
authors.forename: L L
authors.initials: LL
authors.lastname: Daemen
authors.affiliation: Oak Ridge National Laboratory, Spallation Neutron Source, PO Box 2008, MS6475, Oak Ridge, TN 37831-6471, USA.
authors.forename: Y
authors.initials: Y
authors.lastname: Cheng
authors.affiliation: Jacobs University, School of Engineering and Science, Campus Ring 1, 28759 Bremen, Germany.
authors.forename: A
authors.initials: A
authors.lastname: Mavrandonakis
authors.affiliation: Oak Ridge National Laboratory, Spallation Neutron Source, PO Box 2008, MS6475, Oak Ridge, TN 37831-6471, USA.
authors.forename: A J
authors.initials: AJ
authors.lastname: Ramirez-Cuesta
authors.affiliation: Augsburg University, Institute of Physics, Universitätsstr. 1, 86159 Augsburg, Germany.
authors.forename: D
authors.initials: D
authors.lastname: Volkmer
authors.affiliation: Max Planck Institute for Intelligent Systems, Heisenbergstr. 3, 70569 Stuttgart, Germany.
authors.forename: G
authors.initials: G
authors.lastname: Schütz
authors.affiliation: Max Planck Institute for Intelligent Systems, Heisenbergstr. 3, 70569 Stuttgart, Germany.
authors.forename: M
authors.initials: M
authors.lastname: Hirscher
authors.affiliation: Jacobs University, School of Engineering and Science, Campus Ring 1, 28759 Bremen, Germany.|Wilhelm-Ostwald-Institute of Physical and Theoretical Chemistry, Leipzig University, Linnéstr. 2, 04103 Leipzig, Germany.
authors.forename: T
authors.identifier: 0000-0003-2379-6251
authors.initials: T
authors.lastname: Heine