Are Metal–Metal Interactions Involved in the Rising Enthalpies Observed in The Kubas Binding of H2 to Hydrazine-Linked Hydrogen Storage Materials?

Models of two linked M(III) and M(II) (M = Ti, V, Cr) binding sites in hydrazine-linked hydrogen storage materials have been studied quantum chemically using density functional theory. The results compare favorably with previous experimental and computational results. Strong evidence is observed tha...

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Bibliographic Details
Published inJournal of physical chemistry. C Vol. 116; no. 36; pp. 19134 - 19144
Main Authors Skipper, Claire V. J, Antonelli, David M, Kaltsoyannis, Nikolas
Format Journal Article
LanguageEnglish
Published Columbus, OH American Chemical Society 13.09.2012
Subjects
Chemical thermodynamics
Chemistry
Condensed matter: structure, mechanical and thermal properties
Exact sciences and technology
General and physical chemistry
Physics
Thermal properties of condensed matter
Thermal properties of crystalline solids
Thermodynamic properties
Deformation
Ligand
Enthalpy
Theoretical study
Hydrides
Transition metal
Binding site
Coverage rate
Experimental result
Pressure effect
Density functional method
Hydrogen storage material
Hydrazine
Thermodynamic properties
Interaction energy
Quantum theory
Conformation
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Summary:Models of two linked M(III) and M(II) (M = Ti, V, Cr) binding sites in hydrazine-linked hydrogen storage materials have been studied quantum chemically using density functional theory. The results compare favorably with previous experimental and computational results. Strong evidence is observed that the H2 molecules bind to the metal in a Kubas manner. As seen previously in monometallic analogues, , altering the transition metal across the first row of the periodic table reduces the number of H2 molecules that can be bound, and replacing a hydrazide ligand with a hydride increases the M-H2 interaction energy. Evidence is presented for metal–metal interactions, which can influence the H2 binding enthalpy and may help to explain the observed metallic properties and rising H2 binding enthalpies with coverage of the experimental materials. An alternate explanation for the rising enthalpies is also proposed, involving a pressure-induced deformation of the structure with concomitant twisting of the bonds into conformations that allow more optimal binding of an H2 ligand.
ISSN:1932-7447
1932-7455
DOI:10.1021/jp3051643