Reversing the Irreversible: Thermodynamic Stabilization of LiAlH₄ Nanoconfined Within a Nitrogen-Doped Carbon Host

A general problem when designing functional nanomaterials for energy storage is the lack of control over the stability and reactivity of metastable phases. Using the high-capacity hydrogen storage candidate LiAlH₄ as an exemplar, we demonstrate an alternative approach to the thermodynamic stabilization of metastable metal hydrides by coordination to nitrogen binding sites within the nanopores of N-doped CMK-3 carbon (NCMK-3). The resulting LiAlH₄@NCMK-3 material releases H₂ at temperatures as low as 126 °C with full decomposition below 240 °C, bypassing the usual Li₃AlH₆ intermediate observed in bulk. Moreover, >80% of LiAlH₄ can be regenerated under 100 MPa H₂, a feat previously thought to be impossible. Nitrogen sites are critical to these improvements, as no reversibility is observed with undoped CMK-3. Density functional theory predicts a drastically reduced Al-H bond dissociation energy and supports the observed change in the reaction pathway. The calculations also provide a rationale for the solid-state reversibility, which derives from the combined effects of nanoconfinement, Li adatom formation, and charge redistribution between the metal hydride and the host.