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author:

Zhang, L. (Zhang, L..) [1] | Cai, Y. (Cai, Y..) [2] | Li, Y. (Li, Y..) [3] | Sun, C. (Sun, C..) [4] | Xiao, Y. (Xiao, Y..) [5] | Yang, Y. (Yang, Y..) [6] | Chen, D. (Chen, D..) [7] | Xiao, D. (Xiao, D..) [8] | Lee, C.-F. (Lee, C.-F..) [9] | Wang, Y. (Wang, Y..) [10] | Feng, S. (Feng, S..) [11] | Wang, H.-T. (Wang, H.-T..) [12] | Shao, Y.-C. (Shao, Y.-C..) [13] | Chan, T.-S. (Chan, T.-S..) [14] | Ishii, H. (Ishii, H..) [15] | Hiraoka, N. (Hiraoka, N..) [16] | Wang, X. (Wang, X..) [17] | Luo, J. (Luo, J..) [18] | Han, L. (Han, L..) [19]

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Abstract:

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 mgNH 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. © 2025 The Royal Society of Chemistry.

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  • [ 1 ] [Zhang L.]State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, 350002, China
  • [ 2 ] [Cai Y.]State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, 350002, China
  • [ 3 ] [Li Y.]State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, 350002, China
  • [ 4 ] [Sun C.]State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, 350002, China
  • [ 5 ] [Xiao Y.]State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, 350002, China
  • [ 6 ] [Yang Y.]State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, 350002, China
  • [ 7 ] [Chen D.]State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, 350002, China
  • [ 8 ] [Xiao D.]Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing, 100190, China
  • [ 9 ] [Lee C.-F.]Department of Physics, Tamkang University, New Taipei City, 251301, Taiwan
  • [ 10 ] [Wang Y.]State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, 350002, China
  • [ 11 ] [Feng S.]State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, 350002, China
  • [ 12 ] [Wang H.-T.]Department of Physics, Tamkang University, New Taipei City, 251301, Taiwan
  • [ 13 ] [Shao Y.-C.]National Synchrotron Radiation Research Center, Hsinchu, 300092, Taiwan
  • [ 14 ] [Chan T.-S.]National Synchrotron Radiation Research Center, Hsinchu, 300092, Taiwan
  • [ 15 ] [Ishii H.]National Synchrotron Radiation Research Center, Hsinchu, 300092, Taiwan
  • [ 16 ] [Hiraoka N.]National Synchrotron Radiation Research Center, Hsinchu, 300092, Taiwan
  • [ 17 ] [Wang X.]National Engineering Research Center of Chemical Fertilizer Catalyst, Fuzhou University, Fuzhou, 350002, China
  • [ 18 ] [Luo J.]ShenSi Lab, Shenzhen Institute for Advanced Study, University of Electronic Science and Technology of China, Longhua District, Shenzhen, 518110, China
  • [ 19 ] [Han L.]State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, 350002, China

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Source :

Energy and Environmental Science

ISSN: 1754-5692

Year: 2025

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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Chinese Cited Count:

30 Days PV: 2

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