Solid-State NMR Studies of the Local Structure of NaAlH4/C Nanocomposites at Different Stages of Hydrogen Desorption and Rehydrogenation

Structural properties of NaAlH4/C nanocomposites were studied using 23Na and 27Al solid-state NMR. The samples were synthesized by melt infiltration of a highly porous carbon support, with typical pore sizes of 2−3 nm. Physical mixtures of high surface carbon with alanates in different stages of hydrogen desorption show somewhat broadened resonances and a small negative chemical shift compared to pure alanates. This is most likely caused by a susceptibility effect of the carbon support material, which shields and distorts the applied magnetic field. After melt infiltration, 23Na and 27Al spectra are broadened with a small downfield average shift, which is mainly caused by a chemical shift distribution and is explained by a larger disorder in the nanoconfined materials and a possible charge transfer to the carbon. Our measurements show that the local structure of the nanoconfined alanate is the similar to bulk alanate because a comparable chemical shift and average quadrupolar coupling constant is found. In contrast to bulk alanates, in partly desorbed nanocomposite samples no Na3AlH6 is detected. Together with a single release peak observed by dehydrogenation experiments, this points toward a desorption in one single step. 23Na spectra of completely desorbed NaAlH4/C and NaH/C nanocomposites confirm the formation of metallic sodium at lower temperatures than those observed for bulk alanates. The structural properties observed with solid-state NMR of the nanoconfined alanate are restored after a rehydrogenation cycle. This demonstrates that the dehydrogenation of the NaAlH4/C nanocomposite is reversible, even without a Ti-based catalyst.