Ship-in-a-Bottle Synthesis of High Concentration of N₂ Molecules in a Cage-Structured Electride

We report the formation of neutral nitrogen molecules in the cages of [Ca12Al14O32]2+ (C12A7) framework compensated by extra-framework anions. NH3 treatment of C12A7 electride (C12A7:e-) at 800 °C leads to the formation of N2 and NH2- species in the C12A7 cages. N2 and NHx species in the cages are identified using the Raman spectroscopy of 14NH3 and 15NH3-treated C12A7:e-. The concentration of H and N in the C12A7 cages after NH3 treatment is ∼1021 cm-3. We propose a two-step mechanism, supported by density functional theory (DFT) modeling, of N2 incorporation into the C12A7 cages, i.e., incorporation of NH2- formed from decomposition of NH3 at C12A7:e- surface followed by the NH2- species reacting to form N2 molecules. Encapsulation of neutral molecules, as opposed to negatively charged species reported in C12A7 previously, offers new opportunities for trapping and storing gaseous substances in nanoporous materials.