Boosted charge and proton transfer over ternary Co/Co3O4/CoB for electrochemical nitric oxide reduction to ammonia

Xiaoxuan Fan; Zhenyuan Teng; Lupeng Han; Yongjie Shen; Xiyang Wang; Wenqiang Qu; Jialing Song; Zhenlin Wang; Haiyan Duan; Yimin A. Wu; Bin Liu; Dengsong Zhang

doi:10.1038/s41467-025-60043-6

Boosted charge and proton transfer over ternary Co/Co₃O₄/CoB for electrochemical nitric oxide reduction to ammonia

Xiaoxuan Fan, Zhenyuan Teng, Lupeng Han^*, Yongjie Shen, Xiyang Wang, Wenqiang Qu, Jialing Song, Zhenlin Wang, Haiyan Duan, Yimin A. Wu, Bin Liu^*, Dengsong Zhang^*

^*Corresponding author for this work

Research output: Journal Publications and Reviews › RGC 21 - Publication in refereed journal › peer-review

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Abstract

The electrochemical nitric oxide reduction reaction (NORR) holds a great potential for removing environmental pollutant NO and meanwhile generating high value-added ammonia (NH₃). Herein, we tactfully design and synthesize a ternary Co/Co₃O₄/CoB heterostructure that displays a high NH3 Faradaic efficiency of 98.8% in NORR with an NH3 yield rate of 462.18 µmol cm⁻² h⁻¹ (2.31 mol h⁻¹ g_cat⁻¹) at −0.5 V versus reversible hydrogen electrode, outperforming most of the reported NORR electrocatalysts to date. The superior NORR performance is attributed to the enhanced charge and proton transfer over the ternary Co/Co₃O₄/CoB heterostructure. The charge transfer between CoB and Co/Co₃O₄ yields electron-deficient Co and electron-rich Co₃O₄. The electron-deficient Co sites boost H₂O dissociation to generate *H while the electron-rich low-coordination Co₃O₄ sites promote NO adsorption. The *H formed on electron-deficient Co sites is more favorable to transfer to electron-rich Co₃O₄ sites adsorbed with NO, facilitating the selective hydrogenation of NO. This study paves the way for designing and developing highly efficient electrocatalysts for electrochemical reduction of NO to NH₃.

© The Author(s) 2025

Original language	English
Article number	4874
Journal	Nature Communications
Volume	16
Online published	26 May 2025
DOIs	https://doi.org/10.1038/s41467-025-60043-6
Publication status	Published - 2025

Funding

The authors gratefully acknowledge financial support from the National Natural Science Foundation of China (22125604 and 22436003 to D.S.Z.), Shanghai Rising-Star Program (22QA1403700 to L.P.H.) and Science and Technology Commission of Shanghai Municipality (23230713700 to D.S.Z.), the City University of Hong Kong startup fund (9020003 to B.L.), ITF–RTH - Global STEM Professorship (9446006 to B.L.), and JC STEM lab of Advanced CO2 Upcycling (9228005 to B.L.). X.Y.W. acknowledges the receipt of support from the CLSI Student Travel Support Program. XAFS spectra were tested at the HXMA beamline of the Canadian Light Source (CLS), a national research facility of the University of Saskatchewan, which is supported by the Canada Foundation for Innovation (CFI), the Natural Sciences and Engineering Research Council (NSERC), the National Research Council (NRC), and the Government of Saskatchewan. The authors thank Shenzhen HUASUAN Technology Co., Ltd for assistance on DFT calculations (https://huasuankeji.com).

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title = "Boosted charge and proton transfer over ternary Co/Co3O4/CoB for electrochemical nitric oxide reduction to ammonia",

abstract = "The electrochemical nitric oxide reduction reaction (NORR) holds a great potential for removing environmental pollutant NO and meanwhile generating high value-added ammonia (NH3). Herein, we tactfully design and synthesize a ternary Co/Co3O4/CoB heterostructure that displays a high NH3 Faradaic efficiency of 98.8% in NORR with an NH3 yield rate of 462.18 µmol cm−2 h−1 (2.31 mol h−1 gcat−1) at −0.5 V versus reversible hydrogen electrode, outperforming most of the reported NORR electrocatalysts to date. The superior NORR performance is attributed to the enhanced charge and proton transfer over the ternary Co/Co3O4/CoB heterostructure. The charge transfer between CoB and Co/Co3O4 yields electron-deficient Co and electron-rich Co3O4. The electron-deficient Co sites boost H2O dissociation to generate *H while the electron-rich low-coordination Co3O4 sites promote NO adsorption. The *H formed on electron-deficient Co sites is more favorable to transfer to electron-rich Co3O4 sites adsorbed with NO, facilitating the selective hydrogenation of NO. This study paves the way for designing and developing highly efficient electrocatalysts for electrochemical reduction of NO to NH3.{\textcopyright} The Author(s) 2025 ",

author = "Xiaoxuan Fan and Zhenyuan Teng and Lupeng Han and Yongjie Shen and Xiyang Wang and Wenqiang Qu and Jialing Song and Zhenlin Wang and Haiyan Duan and Wu, {Yimin A.} and Bin Liu and Dengsong Zhang",

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language = "English",

volume = "16",

journal = "Nature Communications",

issn = "2041-1723",

publisher = "Springer Nature",

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T1 - Boosted charge and proton transfer over ternary Co/Co3O4/CoB for electrochemical nitric oxide reduction to ammonia

AU - Fan, Xiaoxuan

AU - Teng, Zhenyuan

AU - Han, Lupeng

AU - Shen, Yongjie

AU - Wang, Xiyang

AU - Qu, Wenqiang

AU - Song, Jialing

AU - Wang, Zhenlin

AU - Duan, Haiyan

AU - Wu, Yimin A.

AU - Liu, Bin

AU - Zhang, Dengsong

PY - 2025

Y1 - 2025

N2 - The electrochemical nitric oxide reduction reaction (NORR) holds a great potential for removing environmental pollutant NO and meanwhile generating high value-added ammonia (NH3). Herein, we tactfully design and synthesize a ternary Co/Co3O4/CoB heterostructure that displays a high NH3 Faradaic efficiency of 98.8% in NORR with an NH3 yield rate of 462.18 µmol cm−2 h−1 (2.31 mol h−1 gcat−1) at −0.5 V versus reversible hydrogen electrode, outperforming most of the reported NORR electrocatalysts to date. The superior NORR performance is attributed to the enhanced charge and proton transfer over the ternary Co/Co3O4/CoB heterostructure. The charge transfer between CoB and Co/Co3O4 yields electron-deficient Co and electron-rich Co3O4. The electron-deficient Co sites boost H2O dissociation to generate *H while the electron-rich low-coordination Co3O4 sites promote NO adsorption. The *H formed on electron-deficient Co sites is more favorable to transfer to electron-rich Co3O4 sites adsorbed with NO, facilitating the selective hydrogenation of NO. This study paves the way for designing and developing highly efficient electrocatalysts for electrochemical reduction of NO to NH3.© The Author(s) 2025

AB - The electrochemical nitric oxide reduction reaction (NORR) holds a great potential for removing environmental pollutant NO and meanwhile generating high value-added ammonia (NH3). Herein, we tactfully design and synthesize a ternary Co/Co3O4/CoB heterostructure that displays a high NH3 Faradaic efficiency of 98.8% in NORR with an NH3 yield rate of 462.18 µmol cm−2 h−1 (2.31 mol h−1 gcat−1) at −0.5 V versus reversible hydrogen electrode, outperforming most of the reported NORR electrocatalysts to date. The superior NORR performance is attributed to the enhanced charge and proton transfer over the ternary Co/Co3O4/CoB heterostructure. The charge transfer between CoB and Co/Co3O4 yields electron-deficient Co and electron-rich Co3O4. The electron-deficient Co sites boost H2O dissociation to generate *H while the electron-rich low-coordination Co3O4 sites promote NO adsorption. The *H formed on electron-deficient Co sites is more favorable to transfer to electron-rich Co3O4 sites adsorbed with NO, facilitating the selective hydrogenation of NO. This study paves the way for designing and developing highly efficient electrocatalysts for electrochemical reduction of NO to NH3.© The Author(s) 2025

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JF - Nature Communications

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ER -

Boosted charge and proton transfer over ternary Co/Co₃O₄/CoB for electrochemical nitric oxide reduction to ammonia

Abstract

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Don-HKJC: JC STEM Lab of Advanced C02 Upcycling

ITF-RTH: GSP212 - Research Talent Hub

RMGS: On-site Green Hydrogen Production and Storage for Distributed Carbon Neutral Applications

Cite this

Boosted charge and proton transfer over ternary Co/Co3O4/CoB for electrochemical nitric oxide reduction to ammonia

Abstract

Funding

Publisher's Copyright Statement

RGC Funding Information

Access Output

Other Access Options

Permanent Link

Other Files and Links

Fingerprint

Projects

Don-HKJC: JC STEM Lab of Advanced C02 Upcycling

ITF-RTH: GSP212 - Research Talent Hub

RMGS: On-site Green Hydrogen Production and Storage for Distributed Carbon Neutral Applications

Cite this

Boosted charge and proton transfer over ternary Co/Co₃O₄/CoB for electrochemical nitric oxide reduction to ammonia