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Proton-filtering covalent organic frameworks with superior nitrogen penetration flux promote ambient ammonia synthesis

Nature Catalysis volume 4, pages 322–331 (2021)Cite this article

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Abstract

The simultaneous achievement of both high ammonia yield and Faradaic efficiency in electrochemical nitrogen reduction is a long-sought-after goal. However, due to the strong competing hydrogen evolution and extremely low solubility of N2 in aqueous systems, thermodynamic modulation at the catalyst level is insufficient, leaving the current performance still far from practical application. Here, we rationally control the diffusion of the reactants to obtain suppressed proton supply and greatly enhanced nitrogen flux using proton-filtering covalent organic frameworks, forcing a highly selective and active nitrogen reduction. In this proof-of-concept system, we achieved a high performance in the electrochemical ammonia synthesis (ammonia yield rate 287.2 ± 10.0 μg h−1 \({\rm{mg}}_{\rm{cat.}}^{-1}\), Faradaic efficiency 54.5 ± 1.1%) using a traditional carbon-based catalyst. The proposed strategy successfully optimizes the mass transfer that greatly facilitates nitrogen reduction, providing powerful guidelines for achieving green ammonia production at a more practical level.

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Fig. 1: MD simulations and experimental verifications of the H+ diffusion.
Fig. 2: MD simulations and experimental verifications of the N2 diffusion.
Fig. 3: In situ characterization and electrochemical responses.
Fig. 4: Electroreduction of N2 to NH3 under ambient conditions.

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Data availability

The data that support the findings of this study are available within the article and its Supplementary Information files or from the corresponding author upon reasonable request. Source data are provided with this paper.

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Acknowledgements

We thank J. Ye from the Tan Kah Kee Innovation Laboratory for helping us with the measurements. We also thank the beam line at the National Synchrotron Radiation Research Centre in Taiwan for helping us with the X-ray absorption spectroscopy experiments. We acknowledge the support from the National Natural Science Foundation of China (grant nos. 21703149, 51622208, 51872193 and 5192500409) and Natural Science Foundation of Jiangsu Province (grant nos. BK20190827 and BK20181168).

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Author notes

  1. These authors contributed equally: Sisi Liu, Tao Qian, Mengfan Wang.

Authors and Affiliations

  1. College of Energy, Key Laboratory of Advanced Carbon Materials and Wearable Energy Technologies of Jiangsu Province, Soochow University, Suzhou, China

    Sisi Liu, Tao Qian, Mengfan Wang, Haoqing Ji, Xiaowei Shen, Chao Wang & Chenglin Yan

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  1. Sisi Liu
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Contributions

C.Y. conceived and designed this work. S.L., T.Q. and M.W. prepared the materials and performed the material characterization and electrochemical measurements. H.J. conducted the theoretical calculations. X.S. and C.W. helped with the material characterizations. All authors discussed the results and commented on the article.

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Correspondence to Chenglin Yan.

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The authors declare no competing interests.

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Peer review information Nature Catalysis thanks Matteo Cargnello, Anna Klinkova, Chenghua Sun and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary Figs. 1–42 and Tables 1–11.

Supplementary Data 1

Initial and final configurations of the systems in MD simulations.

Supplementary Data 2

The atomic coordinates of the optimized computational models for density functional theory calculations.

Supplementary Data 3

Source data for Supplementary Figs. 12 and 31–35.

Source data

Source Data Fig. 1

Source data for plotting the curves and symbols.

Source Data Fig. 2

Source data for plotting the curves and symbols.

Source Data Fig. 3

Source data for plotting the curves and symbols.

Source Data Fig. 4

Source data for plotting the curves and symbols.

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Liu, S., Qian, T., Wang, M. et al. Proton-filtering covalent organic frameworks with superior nitrogen penetration flux promote ambient ammonia synthesis. Nat Catal 4, 322–331 (2021). https://doi.org/10.1038/s41929-021-00599-w

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