Electrosynthesis of Ammonia from Nitrate Using a Self-Activated Carbon Fiber Paper

While electrochemically upcycling nitrate wastes to valuable ammonia is considered a very promising pathway for tackling the environmental and energy challenges underlying the nitrogen cycle, the effective catalysts involved are mainly limited to metal-based materials. Here, we report that commercial carbon fiber paper, which is a classical current collector and is typically assumed to be electrochemically inert, can be significantly activated during the reaction. As a result, it shows a high NH₃ Faradaic efficiency of 87.39% at an industrial-level current density of 300 mA cm^-2 for over 90 h of continuous operation, with a NH₃ production rate of as high as 1.22 mmol cm^-2 h^-1. Through experimental and theoretical analysis, the in situ-formed oxygen functional groups are demonstrated to be responsible for the NO₃RR performance. Among them, the C-O-C group is finally identified as the active center, which lowers the thermodynamic energy barrier and simultaneously improves the hydrogenation kinetics. Moreover, high-purity NH₄Cl and NH₃·H₂O were obtained by coupling the NO₃RR with an air-stripping approach, providing an effective way for converting nitrate waste into high-value-added NH₃ products.