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Atomically dispersed bimetallic Fe–Co electrocatalysts for green production of ammonia

Nature Sustainability volume 6, pages 169–179 (2023)Cite this article

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Abstract

The dominant Haber–Bosch process to produce ammonia, arguably the most important chemical in support of global food supply, is both energy and carbon intensive, resulting in substantial environmental impacts. Electrocatalytic nitrogen reduction reaction (NRR) powered by renewable electricity provides a green synthetic route for ammonia, but still suffers from insufficient yield rate and Faradaic efficiency. Single-atom electrocatalysts (SACs) have the potential to transform this catalytic process; however, controllable synthesis of SACs with high loading of active sites remains a big challenge. Here we utilize bacterial cellulose with rich oxygen functional groups to anchor iron (Fe) and cobalt (Co), realizing high density, atomically dispersed, bimetallic Fe–Co active sites. For electrocatalytic NRR, our catalyst design delivers a remarkable ammonia yield rate of 579.2 ± 27.8 μg h−1 mgcat.−1 and an exceptional Faradaic efficiency of 79.0 ± 3.8%. The combined theoretical and experimental investigations reveal that the operando change in coordination configuration from [(O-C2)3Fe–Co(O-C2)3] to [(O-C2)3Fe–Co(O-C)C2] is the enabling chemistry. Our findings suggest a general approach to engineer SACs that can drive critical reactions of relevance for sustainability.

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Fig. 1: Controllable synthesis of bimetallic Fe–Co SAs.
Fig. 2: Bimetallic Fe–Co site configuration.
Fig. 3: NRR performance on the electrocatalyst-loaded GC disk electrode with a loading density of 0.50 mg cm−2.
Fig. 4: NRR performance on GC plate electrode.
Fig. 5: NRR activity origin of bimetallic Fe–Co site.

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Data availability

All data that support the findings in this paper are available within the article and its Supplementary Information. Source data are available from the corresponding author upon reasonable request.

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Acknowledgements

H.Z. acknowledges funding support from the Natural Science Foundation of China (grant no. 52172106 and 51872292). M.H. acknowledges funding support from the Natural Science Foundation of China (grant no. 61804154). Y.L. acknowledges funding support from the Natural Science Foundation of China (grant no. 52122212), Youth Innovation Promotion Association of the CAS (grant no. 2020458) and National Key Research and Development Program of China (grant no. 2019YFA0307900). S.Z. acknowledges funding support from Anhui Provincial Natural Science Foundation (grant no. 2108085QB60), CASHIPS Director’s Fund (grant no. YZJJ2021QN18), China Postdoctoral Science Foundation (grant no. 2020M682057) and Special Research Assistant Program, Chinese Academy of Sciences. This work is also supported by the CAS/SAFEA International Partnership Program for Creative Research Teams of Chinese Academy of Sciences, China. This work was carried out with the support of 1W1B beamline at Beijing Synchrotron Radiation Facility. The computation work was carried out at LvLiang Cloud Computing Centre of China and the DFT calculations were performed on TianHe-2.

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Author notes

  1. These authors contributed equally: Shengbo Zhang, Miaomiao Han, Tongfei Shi.

Authors and Affiliations

  1. Key Laboratory of Materials Physics, Centre for Environmental and Energy Nanomaterials, Anhui Key Laboratory of Nanomaterials and Nanotechnology, CAS Center for Excellence in Nanoscience, Institute of Solid State Physics, HFIPS, Chinese Academy of Sciences, Hefei, China

    Shengbo Zhang, Tongfei Shi, Haimin Zhang, Hongjian Zhou, Chun Chen, Yunxia Zhang, Guozhong Wang & Huajie Yin

  2. University of Science and Technology of China, Hefei, China

    Shengbo Zhang, Tongfei Shi, Haimin Zhang, Hongjian Zhou, Chun Chen, Yunxia Zhang, Guozhong Wang & Huajie Yin

  3. School of Science, Huzhou University, Huzhou, China

    Miaomiao Han

  4. Hefei National Research Center for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei, China

    Yue Lin

  5. National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei, China

    Xusheng Zheng

  6. Beijing Synchrotron Radiation Facility, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing, China

    Li Rong Zheng

  7. Centre for Catalysis and Clean Energy, Griffith University, Gold Coast Campus, Southport, Queensland, Australia

    Huijun Zhao

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Contributions

H. Zhao and H. Zhang conceived the concept and designed the experiments. S.Z. fabricated the catalysts and performed the material characterization and electrochemical measurements. M.H. conducted DFT calculations. L.R.Z. carried out the EXAFS measurements and T.S. analysed the EXAFS results. Y.L. performed the STEM measurements. X.Z., H. Zhou, C.C., Y.Z., G.W. and H.Y. contributed to the experimental design. H. Zhao and H. Zhang supervised the research. H. Zhao, H. Zhang and S.Z. co-wrote the manuscript. All authors discussed the results and commented on the manuscript.

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Correspondence to Haimin Zhang or Huijun Zhao.

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Nature Sustainability thanks Rui Si and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary Figs. 1–39, Tables 1–6 and refs. 1–69.

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Zhang, S., Han, M., Shi, T. et al. Atomically dispersed bimetallic Fe–Co electrocatalysts for green production of ammonia. Nat Sustain 6, 169–179 (2023). https://doi.org/10.1038/s41893-022-00993-7

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