Photon-Phonon Co-Driven Ammonia Synthesis Over Ru/BaTiO3 Under Very Mild Conditions.

Ammonia, as an emerging energy carrier, holds significant strategic importance in the transition of future energy systems. Although the Haber-Bosch process remains the dominant industrial route for ammonia synthesis, its high energy demand and substantial carbon emissions underscore the urgent need for sustainable alternatives. Herein, ruthenium (Ru) with an average particle size of 0.9 nm supported on BaTiO3 is developed, which enables photon-phonon co-driven ammonia synthesis at low temperature and pressure. Photon-generated electrons effectively mitigate the H2 poisoning effect and more importantly remarkably promote N2 adsorption and dissociation on Ru sites, thereby working together with phonons to accelerate hydrogenation along the dissociative pathway. As a result, the ammonia synthesis rate reaches 746.6 mmol gRu -1 h-1 at 350 °C under ambient pressure and 2269 mmol gRu -1 h-1 under 2 MPa via photon-phonon co-driven catalysis, representing a very low apparent activation energy of 24 kJ mol-1 and a 51-fold improvement compared to conventional photocatalysis while maintaining reaction stability for 120 h. This work provides a novel approach toward green ammonia synthesis and opens new avenues for advancing beyond the fossil fuel driven Haber-Bosch process.