Sustainable Ammonia Electrosynthesis Coupled With Glycerol Valorization via an Adaptive Tri‐Component Catalyst

Electrochemical nitrate reduction represents a promising route for sustainable ammonia (NH₃) production, yet its practical deployment is constrained by the limited efficiency of state-of-the-art electrocatalysts and immature system architectures. Here, we report a generalist copper-nickel-tungsten tri-component tandem electrocatalyst via a sequential microwave-hydrothermal deposition route. Under pulsed electrolysis conditions, the catalyst delivers a remarkable Faradaic efficiency of 97.1% and a record-high ammonia yield rate of 43.87 mg h^-1 cm^-2. Online differential electrochemical mass spectrometry (DEMS) identifies key intermediates and associated pathways, while density functional theory (DFT) calculations elucidate the cooperative roles of each component: the copper component facilitates nitrate adsorption and deoxygenation, the nickel component promotes water dissociation for steady *H supply, and the tungsten component serves as a dynamic *H reservoir. This synergy efficiently suppresses hydrogen evolution and enhances ammonia selectivity. Furthermore, coupling with glycerol valorization (to formic acid) as the anodic reaction demonstrates the potential for energy-efficient ammonia electrosynthesis. Collectively, this work offers both design strategies and mechanistic understanding for next-generation multi-component tandem electrocatalysts targeting advanced nitrogen-based chemical synthesis.