Understanding the role of Ti in reversible hydrogen storage as sodium alanate: A combined experimental and density functional theoretical approach

Santanu Chaudhuri, Jason Graetz, Alex Ignatov, James J. Reilly, James Muckerman

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Abstract

We report the results of an experimental and theoretical study of hydrogen storage in sodium alanate (NaAlH4). Reversible hydrogen storage in this material is dependent on the presence of 2-4% Ti dopant. Our combined study shows that the role of Ti may be linked entirely to Ti-containing active catalytic sites in the metallic A1 phase present in the dehydrogenated NaAlH4. The EXAFS data presented here show that dehydrogenated samples contain a highly disordered distribution of Ti-Al distances with no long-range order beyond the second coordination sphere. We have used density functional theory techniques to calculate the chemical potential of possible Ti arrangements on an Al(001) surface for Ti coverages ranging from 0.125 to 0.5 monolayer (ML) and have identified those that can chemisorb molecular hydrogen via spontaneous or only moderately activated pathways. The chemisorption process exhibits a characteristic nodal symmetry property for the low-barrier sites: the incipient doped surface-H2 adduct's highest occupied molecular orbital (HOMO) incorporates the σ* antibonding molecular orbital of hydrogen, allowing the transfer of charge density from the surface to dissociate the molecular hydrogen. This work also proposes a plausible mechanism for the transport of an aluminum hydride species back into the NaH lattice that is supported by Car-Parrinello molecular dynamics (CPMD) simulations of the stability and mobility of aluminum clusters (alanes) on Al(001). As an experimental validation of the proposed role of titanium and the subsequent diffusion of alanes, we demonstrate experimentally that AlH3 sources reacts with NaH to form NaAlH4 without any requirement of a catalyst or hydrogen overpressure.

Original languageEnglish
Pages (from-to)11404-11415
Number of pages12
JournalJournal of the American Chemical Society
Volume128
Issue number35
DOIs
Publication statusPublished - Sep 6 2006

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Hydrogen storage
Hydrogen
Sodium
Molecular orbitals
Aluminum
Chemical potential
Catalytic Domain
Chemisorption
Titanium
Charge density
Hydrides
Density functional theory
Molecular dynamics
Monolayers
Railroad cars
Doping (additives)
Molecular Dynamics Simulation
Catalysts
sodium aluminum hydride
Computer simulation

ASJC Scopus subject areas

  • Chemistry(all)

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Understanding the role of Ti in reversible hydrogen storage as sodium alanate : A combined experimental and density functional theoretical approach. / Chaudhuri, Santanu; Graetz, Jason; Ignatov, Alex; Reilly, James J.; Muckerman, James.

In: Journal of the American Chemical Society, Vol. 128, No. 35, 06.09.2006, p. 11404-11415.

Research output: Contribution to journalArticle

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