Subnanometric alkaline-earth oxide clusters for sustainable nitrate to ammonia photosynthesis

The limitation of inert N₂ molecules with their high dissociation energy has ignited research interests in probing other nitrogen-containing species for ammonia synthesis. Nitrate ions, as an alternative feedstock with high solubility and proton affinity, can be facilely dissociated for sustainable ammonia production. Here we report a nitrate to ammonia photosynthesis route (NO₃⁻RR) catalyzed by subnanometric alkaline-earth oxide clusters. The catalyst exhibits a high ammonia photosynthesis rate of 11.97 mol g_metal⁻¹ h⁻¹ (89.79 mmol g_cat⁻¹ h⁻¹) with nearly 100% selectivity. A total ammonia yield of 0.78 mmol within 72 h is achieved, which exhibits a significant advantage in the area of photocatalytic NO₃⁻RR. The investigation of the molecular-level reaction mechanism reveals that the unique active interface between the subnanometric clusters and TiO₂ substrate is beneficial for the nitrate activation and dissociation, contributing to efficient and selective nitrate reduction for ammonia production with low energy input. The practical application of NO₃⁻RR route in simulated wastewater is developed, which demonstrates great potential for its industrial application. These findings are of general knowledge for the functional development of clusters-based catalysts and could open up a path in the exploitation of advanced ammonia synthesis routes with low energy consumption and carbon emission.