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Nitrate electroreduction to ammonia holds great promise in sustainable green ammonia synthesis, yet faces a dearth of competent electrocatalysts adapted to varying nitrate concentration, and inadequate ammonia fixation. Herein, we present a high-performance Ag single-atom-decorated Cu2O nanowire catalyst (Ag1@Cu2O) that exhibits concentration-universal high-rate nitrate reduction, achieving >90% to near-unity ammonia faradaic efficiency (FE) across nitrate concentrations from 0.01 to 0.5 M. Notably, at 0.5 M nitrate concentration, it attains a two-ampere-level current density (2.3 A cm-2) at -1 V vs. RHE, resulting in a leading ammonia yield rate of 184.4 mgNH3 h-1 cm-2. In situ studies combined with theoretical calculations elucidate an Ag-Cu inter-site synergistic catalytic mechanism, in which single-atom Ag serves as an accelerator for active hydrogen generation and stabilization on Cu sites to boost the hydrogenation kinetics of N-containing intermediates, thus smoothing the energy barriers for ammonia production via the favorable *NHO pathway. Additionally, Ag1@Cu2O demonstrates near-unity formate FE for formaldehyde oxidation, reaching a 300 mA cm-2 current density at a mere 0.31 V vs. RHE. Motivated by this exceptional bifunctionality, we demonstrate an innovative tandem electrochemical-chemical strategy for upgrading ammonia into high-value ammonium formate by coupled electrolysis of nitrate reduction and formaldehyde oxidation, followed by straightforward chemical combination and isolation. In practice, membrane electrode assembly (MEA) electrolysis at 1.6 V for 100 h successfully outputs 10.7 g of high-purity ammonium formate. Furthermore, the commonality of this strategy is validated by application to various nitrate/aldehyde pairs. This work blazes a new trail for scalable, cost- and energy-efficient green ammonia production and fixation from nitrate reduction.
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ENERGY & ENVIRONMENTAL SCIENCE
ISSN: 1754-5692
Year: 2025
Issue: 6
Volume: 18
3 2 . 4 0 0
JCR@2023
CAS Journal Grade:1
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ESI Highly Cited Papers on the List: 0 Unfold All
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30 Days PV: 1