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Updated: Oct 22, 2025

Supercritical Nitrogen Processing for the Purification of Reactive Porous Materials
Published on: May 15, 2015
Defying Thermodynamics: Stabilization of Alane Within Covalent Triazine Frameworks for Reversible Hydrogen Storage
Vitalie Stavila1, Sichi Li2, Chaochao Dun3
1Sandia National Laboratories, 7011 East Avenue, Livermore, CA, 94550, USA.
Abstract:
The highly unfavorable thermodynamics of direct aluminum hydrogenation can be overcome by stabilizing alane within a nanoporous bipyridine-functionalized covalent triazine framework (AlH3 @CTF-bipyridine). This material and the counterpart AlH3 @CTF-biphenyl rapidly desorb H2 between 95 and 154 °C, with desorption complete at 250 °C. Sieverts measurements, 27 Al MAS NMR and 27 Al{1 H} REDOR experiments, and computational spectroscopy reveal that AlH3 @CTF-bipyridine dehydrogenation is reversible at 60 °C under 700 bar hydrogen, >10 times lower pressure than that required to hydrogenate bulk aluminum. DFT calculations and EPR measurements support an unconventional mechanism whereby strong AlH3 binding to bipyridine results in single-electron transfer to form AlH2 (AlH3 )n clusters. The resulting size-dependent charge redistribution alters the dehydrogenation/rehydrogenation thermochemistry, suggesting a novel strategy to enable reversibility in high-capacity metal hydrides.
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