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

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.

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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).

Author information

Correspondence to Wen-Jie Jiang or Jin-Song Hu.

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Dedications

This article is dedicated to Professor Charles M. Lieber in celebration of his 60th birthday. Worked with honor for 3 years under the supervision of Charlie in nanoplatform-enabled fundamental understanding of energy devices, J. S. H. gratefully acknowledges all the inspiration from Charlie that encourages to “think harder and work smarter” in persistently pursuing true science.

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Yuan, L., Wu, Z., Jiang, W. et al. Phosphorus-doping activates carbon nanotubes for efficient electroreduction of nitrogen to ammonia. Nano Res. (2020) doi:10.1007/s12274-020-2637-8

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Keywords

  • P-doped carbon nanotubes
  • nitrogen reduction reaction
  • active sites
  • reaction pathway
  • electrocatalysis