Cross‐Interfacial Electron Bridge‐Driven Dynamic Reconstruction Breaks Hydrogenation Limitations to Accelerate Ammonia Synthesis

ABSTRACT Ammonia bridges sustainable agriculture and carbon‐neutral energy systems, with electrocatalytic nitrate‐to‐ammonia (NO 3 − ‐to‐NH 3 ) conversion now offering a dual‐action solution for decentralized nitrogen recovery and renewable energy storage. However, the energy efficiency is limited by the sluggish rate‐determining step (RDS) of nitrate‐to‐nitrite (NO 3 − ‐to‐NO 2 − ) conversion and NO 2 − ‐to‐NH 3 hydrogenation. Here we propose a cross‐interfacial electron bridges (CIEBs)‐enabled electrochemical in situ electronic reconstruction strategy that circumvents conventional RDS, achieving enhanced NO 3 − ‐to‐NH 3 conversion efficiency. Pt‐Cu phosphide heterointerfaces (Cu‐Pt‐P) were designed and adopted as model catalysts. The Cu redox cycling drives spontaneous NO 3 − ‐to‐NH 3 conversion, while Pt sites mediate in situ electronic reconstruction via CIEBs, enabling continuous regeneration of active Cu species together with a sustained *H supply for efficient NH 3 production. This unconventional reaction pathway demonstrates exceptional catalytic performance in a sequencing batch NO 3 RR‐OER electrolyzer device, achieving an NH 3 production rate of 31.63 mg cm −2 h −1 with 96.4% Faradaic efficiency (FE) at 120 mA cm −2 while reducing operational expenditures for nitrogenous wastewater remediation. This electronic reconstruction principle establishes a universal CIEBs design framework that bridges efficient electrocatalysis with sustainable wastewater nutrient recovery.