Hydrazine‐Mediated Thermally Assisted Photocatalytic Ammonia Decomposition Over Layered Protonated Perovskites

Photocatalytic ammonia decomposition offers a sustainable route for hydrogen production, but its development is limited by low catalytic efficiency and poorly understood mechanisms. Here, a protonated layered perovskite, HPrNb₂O₇ (HPNO), is reported as an efficient catalyst for ammonia decomposition under mild photo-thermal conditions. Upon exposure to NH₃ at elevated temperatures, HPNO promotes the in situ formation and intercalation of hydrazine intermediates within its interlayer galleries, enabled by thermally generated oxygen vacancies and hydrogen bonding. Advanced characterization techniques have been applied to confirm the formation and stabilization of hydrazine. It is also shown that thermal energy prolongs charge carrier lifetimes and enhances oxygen vacancy formation, contributing to a strong photo-thermal synergy. The stabilization of hydrazine intermediate promotes the associative mechanism, lowering the activation barrier, thus leading to an enhanced hydrogen evolution rate of 1311.2 µmol·g^-1·h^-1 at 200 °C under simulated solar irradiation without any noble metal co-catalyst. This work reveals a distinct, hydrazine-mediated reaction pathway and positions layered protonated perovskites as promising materials for efficient, solar-driven ammonia decomposition and sustainable hydrogen generation.