Highly dispersed Pt boosts active Fe N formation in ammonia decomposition

Ammonia decomposition plays an important role in hydrogen production, especially in the context of a hydrogen economy. Fe-based catalysts are a popular choice due to their affordability and moderate activity, making them attractive for large-scale applications. However, the transformation of Fe-based catalysts into more active FexN species can be slow, resulting in a prolonged induction period. To address this issue, we investigated the effects of Pt addition on FexN formation in ammonia decomposition. Our results show that even a slight Pt addition significantly enhances the FexN formation rate, increasing it over threefold. Pt aids in H2 desorption via reverse spillover, which, in turn, exposes more Fe surface sites where nitridation occurs, leading to the formation of iron nitride. Characterization via High-angle annular dark-field imaging scanning transmission electron microscopy, X-ray diffraction, and in situ X-ray absorption spectroscopy (XAS) revealed the formation of Fe2N as active species, whereas temperature-programmed hydrogen desorption, temperature-programmed reduction by hydrogen, and in situ XAS supported the existence of H reverse spillover and spillover effects. Overall, our study provides an improved understanding of the active species formation mechanism of Fe catalysts in ammonia decomposition and offers a simple strategy for improving their catalytic performance.