Ammonia Synthesis over Fe‐Supported Catalysts Mediated by Face‐Sharing Nitrogen Sites in BaTiO3−xNy Oxynitride

Nitride and hydride materials have been proposed as active supports for the loading of transition metal catalysts in thermal catalytic ammonia synthesis. However, the contribution of nitrogen or hydride anions in the support to the catalytic activity for supported transition-metal catalysts is not well understood, especially for Fe-based catalysts. Here, we report that hexagonal-BaTiO3-x Ny with nitrogen vacancies at face-sharing sites acts as a more efficient support for Fe catalysts for ammonia synthesis than BaTiO3 or BaTiO3-x Hx at 260 °C to 400 °C. Isotopic experiments, in situ measurements, and a small inverse isotopic effect in ammonia synthesis have revealed that nitrogen molecules are activated at nitrogen vacancies formed at the interface between Fe nanoparticles and the support. Nitrogen vacancies on BaTiO3-x Ny can promote the activity of Fe and Ni catalysts, while electron donation and suppression of hydrogen poisoning by BaTiO3-x Hx are significant in the Ru and Co systems.