TY - JOUR
T1 - Toward separation of hydrogen isotopologues by exploiting zero-point energy difference at strongly attractive adsorption site models
AU - Wulf, Toshiki
AU - Heine, Thomas
N1 - Publisher Copyright:
© 2017 Wiley Periodicals, Inc.
Copyright:
Copyright 2018 Elsevier B.V., All rights reserved.
PY - 2018/5/5
Y1 - 2018/5/5
N2 - Recent reports on hydrogen isotope separation in metal-organic frameworks are rationalized by the presence of undercoordinated metal sites. In this work, we screen undercoordinated divalent metals for their performance as hydrogen separating agents in common chemical environments (as free dications, as part of M2(HCOO)4 paddlewheels and in metal porphyrins). We calculate heat of adsorption and selectivity using the Langmuir model and the density-functional-based potential energy surface. Our calculations show a strong metal ion dependence of the adsorption energy in paddlewheels, but rather small impact of metal choice in stable porphyrins. D2-over-H2 selectivities reach top values of 12 for CO2+ paddlewheels, while only oxidatively unstable porphyrins incorporating Cr2+, V2+, and Ti2+ show high selectivities.
AB - Recent reports on hydrogen isotope separation in metal-organic frameworks are rationalized by the presence of undercoordinated metal sites. In this work, we screen undercoordinated divalent metals for their performance as hydrogen separating agents in common chemical environments (as free dications, as part of M2(HCOO)4 paddlewheels and in metal porphyrins). We calculate heat of adsorption and selectivity using the Langmuir model and the density-functional-based potential energy surface. Our calculations show a strong metal ion dependence of the adsorption energy in paddlewheels, but rather small impact of metal choice in stable porphyrins. D2-over-H2 selectivities reach top values of 12 for CO2+ paddlewheels, while only oxidatively unstable porphyrins incorporating Cr2+, V2+, and Ti2+ show high selectivities.
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U2 - 10.1002/qua.25545
DO - 10.1002/qua.25545
M3 - Article
AN - SCOPUS:85034219528
VL - 118
JO - International Journal of Quantum Chemistry
JF - International Journal of Quantum Chemistry
SN - 0020-7608
IS - 9
M1 - e25545
ER -