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Nano Research 2020, 13(5): 1376-1382 https://doi.org/10.1007/s12274-020-2637-8
Research Article | Issue | Published: 15 January 2020

Phosphorus-doping activates carbon nanotubes for efficient electroreduction of nitrogen to ammonia

Show Author's Information Lu-Pan Yuan1,2,  Ze-Yuan Wu1,2,  Wen-Jie Jiang1( ),  Tang Tang1,2,  Shuai Niu1,2,  Jin-Song Hu1,2( )
Beijing National Laboratory for Molecular Sciences (BNLMS), CAS Key Laboratory of Molecular Nanostructure and Nanotechnology, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China
University of Chinese Academy of Sciences, Beijing 100049, China
Keywords:
electrocatalysis, nitrogen reduction reaction, P-doped carbon nanotubes, active sites, reaction pathway
Topics:
Cost effectivenessElectrocatalysis ElectrocatalystsElectrolytic reduction Energy efficiencyKinetic theoryNitrogenOrganic polymersPhosphorus
Cite this article:
Yuan L-P, Wu Z-Y, Jiang W-J, et al. Phosphorus-doping activates carbon nanotubes for efficient electroreduction of nitrogen to ammonia. Nano Research, 2020, 13(5): 1376-1382. https://doi.org/10.1007/s12274-020-2637-8
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Abstract Full text Electronic supplementary material About this article

The electrochemical nitrogen reduction reaction (NRR) as an energy-efficient approach for ammonia synthesis is hampered by the low ammonia yield and ambiguous reaction mechanism. Herein, phosphorus-doped carbon nanotube (P-CNTs) is developed as an efficient metal-free electrocatalyst for NRR with a remarkable NH3 yield of 24.4 μg·h-1·mg-1cat. and partial current density of 0.61 mA·cm-2. Such superior activity is found to be from P doping and highly conjugated CNTs substrate. Experimental and theoretical investigations discover that the electron-deficient phosphorus sites with Lewis acidity should be genuine active sites and NRR on P-CNTs follows the distal pathway. These findings provide insightful understanding on NRR processes on P-CNTs, opening up opportunities for the rational design of highly-active cost-effective metal-free catalysts for electrochemical ammonia synthesis.


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Electronic supplementary material
About this article

Phosphorus-doping activates carbon nanotubes for efficient electroreduction of nitrogen to ammonia

Show Author's information Lu-Pan Yuan1,2, Ze-Yuan Wu1,2, Wen-Jie Jiang1( ), Tang Tang1,2, Shuai Niu1,2, Jin-Song Hu1,2( )
Beijing National Laboratory for Molecular Sciences (BNLMS), CAS Key Laboratory of Molecular Nanostructure and Nanotechnology, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China
University of Chinese Academy of Sciences, Beijing 100049, China

Abstract

The electrochemical nitrogen reduction reaction (NRR) as an energy-efficient approach for ammonia synthesis is hampered by the low ammonia yield and ambiguous reaction mechanism. Herein, phosphorus-doped carbon nanotube (P-CNTs) is developed as an efficient metal-free electrocatalyst for NRR with a remarkable NH3 yield of 24.4 μg·h-1·mg-1cat. and partial current density of 0.61 mA·cm-2. Such superior activity is found to be from P doping and highly conjugated CNTs substrate. Experimental and theoretical investigations discover that the electron-deficient phosphorus sites with Lewis acidity should be genuine active sites and NRR on P-CNTs follows the distal pathway. These findings provide insightful understanding on NRR processes on P-CNTs, opening up opportunities for the rational design of highly-active cost-effective metal-free catalysts for electrochemical ammonia synthesis.

Keywords: electrocatalysis, nitrogen reduction reaction, P-doped carbon nanotubes, active sites, reaction pathway

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Publication history
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Acknowledgements

Publication history

Received: 25 September 2019
Revised: 31 December 2019
Accepted: 02 January 2020
Published: 15 January 2020
Issue date: May 2020

Copyright

© Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature 2020

Acknowledgements

We acknowledge the financial supports are from the National Key Research and Development Program of China (No. 2016YFB0101202), the National Natural Science Foundation of China (Nos. 91645123 and 21773263).

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