Dynamic Photovoltaic‐Electrolysis Coupling of Stable (>1000 h) CuP/CoF Catalysts with 6% Solar‐to‐Fuel Efficiency

Solar-driven ammonia synthesis via electrocatalytic nitrate reduction could disrupt the century-old Haber-Bosch process. However, current systems are limited to lab-scale prototypes due to the instability of photovoltaic-electrolysis (PV-EC) coupling under real-world solar fluctuations and unproven scalability. Here, we present a laboratory to megawatt (Lab-to-MW) framework, encompassing catalyst design and renewable energy-powered ammonia synthesis. A dual-functional CuP/CoF catalyst fabricated on cobalt foam enables efficient nitrate-to-ammonia conversion by modulating reactive hydrogen (^*H) supply and reducing the kinetic barrier for the hydrogenation of nitrogenous intermediates. The catalyst achieves a high ammonia faradaic efficiency of 81.2% at low potential (-0.3 V vs. RHE) and long-term stability (>1000 h) in anion-exchange membrane (AEM) electrolyzers. Subsequently, a dynamic PV-EC system integrating >25%-efficiency silicon solar modules, operates stably for 50 h under simulated irradiance (air mass, AM 1.5G), delivering a 5.92% solar-to-fuel (STF) efficiency under natural ambient conditions. Capitalizing on this foundation, our solar-adaptive techno-economic modeling demonstrates a transformative levelized cost of ammonia (LCOA) at $0.93/kg NH₃ for 1 MW-scale solar ammonia with real-world irradiance adaptability. This work provides a replicable blueprint for decarbonizing industrial ammonia production, redefining the scalability of solar-driven electrocatalysis for sustainable chemical manufacturing.