Toward separation of hydrogen isotopologues by exploiting zero-point energy difference at strongly attractive adsorption site models

Toshiki Wulf; Thomas Heine

doi:10.1002/qua.25545

Toward separation of hydrogen isotopologues by exploiting zero-point energy difference at strongly attractive adsorption site models

Toshiki Wulf, Thomas Heine

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

2 Citations (Scopus)

Abstract

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.

Original language	English
Article number	e25545
Journal	International Journal of Quantum Chemistry
Volume	118
Issue number	9
DOIs	https://doi.org/10.1002/qua.25545
Publication status	Published - 2018 May 5

All Science Journal Classification (ASJC) codes

Atomic and Molecular Physics, and Optics
Condensed Matter Physics
Physical and Theoretical Chemistry

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10.1002/qua.25545

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abstract = "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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AU - Heine, Thomas

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