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

ABSTRACT 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 NH 3 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.