Dual Au-Ti perimeter site engineering enables cooperative N2 activation for efficient electrochemical nitrogen fixation

Ying GUO; Ziyu MEI; Chengkai SHI; Chunfeng WANG; Rong ZHANG; Shaoce ZHANG; Chuangwei LIU; Pongtanawat KHEMTHONG; Jing-Li LUO

doi:10.1016/j.apcatb.2025.126260

Dual Au-Ti perimeter site engineering enables cooperative N₂ activation for efficient electrochemical nitrogen fixation

Ying GUO
, Ziyu MEI
, Chengkai SHI
, Chunfeng WANG
, Rong ZHANG
, Shaoce ZHANG
, Chuangwei LIU^*
, Pongtanawat KHEMTHONG
, Jing-Li LUO^*

^*Corresponding author for this work

School of Interdisciplinary Studies

Research output: Journal Publications › Journal Article (refereed) › peer-review

Abstract

Electrochemical N₂ fixation, including N₂-to-NH₃ (NRR) and N₂-to-NO₃^– (NOR) conversions, represents sustainable alternative to the energy-intensive Harbor-Bosch and Ostwald processes for ammonia and nitrate production, respectively. The key to efficient nitrogen fixation lies in the adsorption and activation of N₂. The heterogenous dual perimeter active sites exhibit higher energetic activity of N₂ activation in favor of the subsequent processes. Herein, we present an Au/TiO₂ catalyst with heterogenous dual Au-Ti perimeter sites for electrochemical N₂ fixation under ambient conditions. The catalyst demonstrates excellent performance in both NH₃ and NO₃^- production with an NH₃ yield of 9.4 μmol cm^-2 h^-1 (FE: 32.2 %), and a NO₃^- yield of 1.4 μmol cm^-2 h^-1 (FE: 33.0 %), along with impressive electrochemical stability, outperforming most reported catalysts. In situ characterizations and theoretical calculations reveal that the N₂ molecules preferentially adsorb on the Au/TiO₂ perimeter, bridging Au and Ti sites in a sloped orientation to form a unique Au-N-N-Ti structure. This configuration significantly activates the adsorbed N₂ molecules by extending the N-N bond length and decreasing its energy, thereby facilitating the narrowed span energies to produce NH₃ and NO₃^-. Our work establishes a novel approach utilizing heterogeneous dual perimeter sites to designing high-performance catalysts for nitrogen fixation.

Original language	English
Article number	126260
Journal	Applied Catalysis B: Environmental
Volume	385
Early online date	29 Nov 2025
DOIs	https://doi.org/10.1016/j.apcatb.2025.126260 https://doi.org/10.1016/j.apcatb.2025.126260
Publication status	E-pub ahead of print - 29 Nov 2025

Bibliographical note

Publisher Copyright:
© 2025 Elsevier B.V.

Funding

This work was financially supported by the Shenzhen Science and Technology Program (No. KQTD20190929173914967 and ZDSYS20220527171401003 ) and further benefited from financial support of Lingnan University , including the Lam Woo Research Fund and a start-up grant. The authors wish to acknowledge the assistance from the Electron Microscope Center of the Shenzhen University in TEM investigations of this work.

Keywords

Ammonia synthesis
Cooperative N Activation
Dual perimeter active sites
Electrochemical dinitrogen, fixation
Nitrate production

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Cite this

GUO, Y., MEI, Z., SHI, C., WANG, C., ZHANG, R., ZHANG, S., LIU, C., KHEMTHONG, P., & LUO, J.-L. (2026). Dual Au-Ti perimeter site engineering enables cooperative N₂ activation for efficient electrochemical nitrogen fixation. Applied Catalysis B: Environmental, 385, Article 126260. Advance online publication. https://doi.org/10.1016/j.apcatb.2025.126260, https://doi.org/10.1016/j.apcatb.2025.126260

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title = "Dual Au-Ti perimeter site engineering enables cooperative N2 activation for efficient electrochemical nitrogen fixation",

abstract = "Electrochemical N2 fixation, including N2-to-NH3 (NRR) and N2-to-NO3– (NOR) conversions, represents sustainable alternative to the energy-intensive Harbor-Bosch and Ostwald processes for ammonia and nitrate production, respectively. The key to efficient nitrogen fixation lies in the adsorption and activation of N2. The heterogenous dual perimeter active sites exhibit higher energetic activity of N2 activation in favor of the subsequent processes. Herein, we present an Au/TiO2 catalyst with heterogenous dual Au-Ti perimeter sites for electrochemical N2 fixation under ambient conditions. The catalyst demonstrates excellent performance in both NH3 and NO3- production with an NH3 yield of 9.4 μmol cm-2 h-1 (FE: 32.2 \%), and a NO3- yield of 1.4 μmol cm-2 h-1 (FE: 33.0 \%), along with impressive electrochemical stability, outperforming most reported catalysts. In situ characterizations and theoretical calculations reveal that the N2 molecules preferentially adsorb on the Au/TiO2 perimeter, bridging Au and Ti sites in a sloped orientation to form a unique Au-N-N-Ti structure. This configuration significantly activates the adsorbed N2 molecules by extending the N-N bond length and decreasing its energy, thereby facilitating the narrowed span energies to produce NH3 and NO3-. Our work establishes a novel approach utilizing heterogeneous dual perimeter sites to designing high-performance catalysts for nitrogen fixation.",

keywords = "Ammonia synthesis, Cooperative N Activation, Dual perimeter active sites, Electrochemical dinitrogen, fixation, Nitrate production",

author = "Ying GUO and Ziyu MEI and Chengkai SHI and Chunfeng WANG and Rong ZHANG and Shaoce ZHANG and Chuangwei LIU and Pongtanawat KHEMTHONG and Jing-Li LUO",

note = "Publisher Copyright: {\textcopyright} 2025 Elsevier B.V.",

year = "2025",

month = nov,

day = "29",

doi = "10.1016/j.apcatb.2025.126260",

language = "English",

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T1 - Dual Au-Ti perimeter site engineering enables cooperative N2 activation for efficient electrochemical nitrogen fixation

AU - GUO, Ying

AU - MEI, Ziyu

AU - SHI, Chengkai

AU - WANG, Chunfeng

AU - ZHANG, Rong

AU - ZHANG, Shaoce

AU - LIU, Chuangwei

AU - KHEMTHONG, Pongtanawat

AU - LUO, Jing-Li

PY - 2025/11/29

Y1 - 2025/11/29

N2 - Electrochemical N2 fixation, including N2-to-NH3 (NRR) and N2-to-NO3– (NOR) conversions, represents sustainable alternative to the energy-intensive Harbor-Bosch and Ostwald processes for ammonia and nitrate production, respectively. The key to efficient nitrogen fixation lies in the adsorption and activation of N2. The heterogenous dual perimeter active sites exhibit higher energetic activity of N2 activation in favor of the subsequent processes. Herein, we present an Au/TiO2 catalyst with heterogenous dual Au-Ti perimeter sites for electrochemical N2 fixation under ambient conditions. The catalyst demonstrates excellent performance in both NH3 and NO3- production with an NH3 yield of 9.4 μmol cm-2 h-1 (FE: 32.2 %), and a NO3- yield of 1.4 μmol cm-2 h-1 (FE: 33.0 %), along with impressive electrochemical stability, outperforming most reported catalysts. In situ characterizations and theoretical calculations reveal that the N2 molecules preferentially adsorb on the Au/TiO2 perimeter, bridging Au and Ti sites in a sloped orientation to form a unique Au-N-N-Ti structure. This configuration significantly activates the adsorbed N2 molecules by extending the N-N bond length and decreasing its energy, thereby facilitating the narrowed span energies to produce NH3 and NO3-. Our work establishes a novel approach utilizing heterogeneous dual perimeter sites to designing high-performance catalysts for nitrogen fixation.

AB - Electrochemical N2 fixation, including N2-to-NH3 (NRR) and N2-to-NO3– (NOR) conversions, represents sustainable alternative to the energy-intensive Harbor-Bosch and Ostwald processes for ammonia and nitrate production, respectively. The key to efficient nitrogen fixation lies in the adsorption and activation of N2. The heterogenous dual perimeter active sites exhibit higher energetic activity of N2 activation in favor of the subsequent processes. Herein, we present an Au/TiO2 catalyst with heterogenous dual Au-Ti perimeter sites for electrochemical N2 fixation under ambient conditions. The catalyst demonstrates excellent performance in both NH3 and NO3- production with an NH3 yield of 9.4 μmol cm-2 h-1 (FE: 32.2 %), and a NO3- yield of 1.4 μmol cm-2 h-1 (FE: 33.0 %), along with impressive electrochemical stability, outperforming most reported catalysts. In situ characterizations and theoretical calculations reveal that the N2 molecules preferentially adsorb on the Au/TiO2 perimeter, bridging Au and Ti sites in a sloped orientation to form a unique Au-N-N-Ti structure. This configuration significantly activates the adsorbed N2 molecules by extending the N-N bond length and decreasing its energy, thereby facilitating the narrowed span energies to produce NH3 and NO3-. Our work establishes a novel approach utilizing heterogeneous dual perimeter sites to designing high-performance catalysts for nitrogen fixation.

KW - Ammonia synthesis

KW - Cooperative N Activation

KW - Dual perimeter active sites

KW - Electrochemical dinitrogen, fixation

KW - Nitrate production

UR - https://www.scopus.com/pages/publications/105023832632

U2 - 10.1016/j.apcatb.2025.126260

DO - 10.1016/j.apcatb.2025.126260

M3 - Journal Article (refereed)

SN - 0926-3373

VL - 385

JO - Applied Catalysis B: Environmental

JF - Applied Catalysis B: Environmental

M1 - 126260

ER -