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author:

Zhang, Linjie (Zhang, Linjie.) [1] | Cai, Yimeng (Cai, Yimeng.) [2] | Li, Yanghua (Li, Yanghua.) [3] | Sun, Chen (Sun, Chen.) [4] | Xiao, Yi (Xiao, Yi.) [5] | Yang, Yibing (Yang, Yibing.) [6] | Chen, Dechao (Chen, Dechao.) [7] | Xiao, Dongdong (Xiao, Dongdong.) [8] | Lee, Chi-Feng (Lee, Chi-Feng.) [9] | Wang, Yunjian (Wang, Yunjian.) [10] | Feng, Shiqiang (Feng, Shiqiang.) [11] | Wang, Hsiao-Tsu (Wang, Hsiao-Tsu.) [12] | Shao, Yu-Cheng (Shao, Yu-Cheng.) [13] | Chan, Ting-Shan (Chan, Ting-Shan.) [14] | Ishii, Hirofumi (Ishii, Hirofumi.) [15] | Hiraoka, Nozomu (Hiraoka, Nozomu.) [16] | Wang, Xiuyun (Wang, Xiuyun.) [17] (Scholars:王秀云) | Luo, Jun (Luo, Jun.) [18] | Han, Lili (Han, Lili.) [19]

Indexed by:

EI Scopus SCIE

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 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.

Keyword:

Community:

  • [ 1 ] [Zhang, Linjie]Chinese Acad Sci, Fujian Inst Res Struct Matter, State Key Lab Struct Chem, Fuzhou 350002, Peoples R China
  • [ 2 ] [Cai, Yimeng]Chinese Acad Sci, Fujian Inst Res Struct Matter, State Key Lab Struct Chem, Fuzhou 350002, Peoples R China
  • [ 3 ] [Li, Yanghua]Chinese Acad Sci, Fujian Inst Res Struct Matter, State Key Lab Struct Chem, Fuzhou 350002, Peoples R China
  • [ 4 ] [Sun, Chen]Chinese Acad Sci, Fujian Inst Res Struct Matter, State Key Lab Struct Chem, Fuzhou 350002, Peoples R China
  • [ 5 ] [Xiao, Yi]Chinese Acad Sci, Fujian Inst Res Struct Matter, State Key Lab Struct Chem, Fuzhou 350002, Peoples R China
  • [ 6 ] [Yang, Yibing]Chinese Acad Sci, Fujian Inst Res Struct Matter, State Key Lab Struct Chem, Fuzhou 350002, Peoples R China
  • [ 7 ] [Chen, Dechao]Chinese Acad Sci, Fujian Inst Res Struct Matter, State Key Lab Struct Chem, Fuzhou 350002, Peoples R China
  • [ 8 ] [Wang, Yunjian]Chinese Acad Sci, Fujian Inst Res Struct Matter, State Key Lab Struct Chem, Fuzhou 350002, Peoples R China
  • [ 9 ] [Feng, Shiqiang]Chinese Acad Sci, Fujian Inst Res Struct Matter, State Key Lab Struct Chem, Fuzhou 350002, Peoples R China
  • [ 10 ] [Han, Lili]Chinese Acad Sci, Fujian Inst Res Struct Matter, State Key Lab Struct Chem, Fuzhou 350002, Peoples R China
  • [ 11 ] [Xiao, Dongdong]Chinese Acad Sci, Beijing Natl Lab Condensed Matter Phys, Inst Phys, Beijing 100190, Peoples R China
  • [ 12 ] [Lee, Chi-Feng]Tamkang Univ, Dept Phys, New Taipei City 251301, Taiwan
  • [ 13 ] [Wang, Hsiao-Tsu]Tamkang Univ, Dept Phys, New Taipei City 251301, Taiwan
  • [ 14 ] [Shao, Yu-Cheng]Natl Synchrotron Radiat Res Ctr, Hsinchu 300092, Taiwan
  • [ 15 ] [Chan, Ting-Shan]Natl Synchrotron Radiat Res Ctr, Hsinchu 300092, Taiwan
  • [ 16 ] [Ishii, Hirofumi]Natl Synchrotron Radiat Res Ctr, Hsinchu 300092, Taiwan
  • [ 17 ] [Hiraoka, Nozomu]Natl Synchrotron Radiat Res Ctr, Hsinchu 300092, Taiwan
  • [ 18 ] [Wang, Xiuyun]Fuzhou Univ, Natl Engn Res Ctr Chem Fertilizer Catalyst, Fuzhou 350002, Peoples R China
  • [ 19 ] [Luo, Jun]Univ Elect Sci & Technol China, Shenzhen Inst Adv Study, ShenSi Lab, Shenzhen 518110, Peoples R China

Reprint 's Address:

  • [Han, Lili]Chinese Acad Sci, Fujian Inst Res Struct Matter, State Key Lab Struct Chem, Fuzhou 350002, Peoples R China

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Source :

ENERGY & ENVIRONMENTAL SCIENCE

ISSN: 1754-5692

Year: 2025

Issue: 6

Volume: 18

3 2 . 4 0 0

JCR@2023

CAS Journal Grade:1

Cited Count:

WoS CC Cited Count:

SCOPUS Cited Count:

ESI Highly Cited Papers on the List: 0 Unfold All

WanFang Cited Count:

Chinese Cited Count:

30 Days PV: 1

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