Mimicking Enzymatic Proton Channeling Enables Near‐Unity Selective Ammonia Electrosynthesis Beyond Neutral Limits

ABSTRACT

Fragmented hydrogen‐bond networks relegate proton transport to sluggish diffusion, leading to mismatched proton supply that compromises catalytic efficiency and selectivity, thereby necessitating strategies to enhance water‐network ordering. Inspired by the proton channel mechanism in enzymatic catalysis, this work anchors silicotungstate (SiW ₁₂ ) onto Co ₃ O ₄ to construct a SiW ₁₂ /Co ₃ O ₄ catalyst. The domain electrostatic field of SiW ₁₂ induces the ordered arrangement of interfacial water molecules, establishing an ordered water channel for proton migration. The results demonstrate that SiW ₁₂ promotes interfacial water activation and alleviates proton‐transfer limitations, enabling rapid and directional proton delivery to nitrogen‐containing intermediates. Leveraging this unique proton channel, SiW ₁₂ /Co ₃ O ₄ achieves near 100% selectivity over a wide potential window (−0.3 to −0.9 V vs. RHE) and a broad nitrate concentration range (0.01–1 M), achieving 99.3% NH ₃ FE and 15.1 mg h ⁻¹ cm ⁻² yield at −0.8 V versus RHE. Furthermore, the assembled Zn–NO ₃ ⁻ battery delivers the highest reported power density (26.1 mW cm ⁻² ) under neutral conditions. This work establishes interfacial solvation‐structure engineering as a general strategy for regulating proton delivery and developing highly selective electrocatalysts for sustainable ammonia electrosynthesis.