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Water oxidation on a mononuclear manganese heterogeneous catalyst

Nature Catalysis volume 1, pages 870–877 (2018)Cite this article

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Abstract

Water oxidation is the prerequisite for dioxygen evolution in natural or artificial photosynthesis. Although it has been demonstrated that multinuclear active sites are commonly necessary for water oxidation, as inspired by the natural oxygen-evolving centre CaMn4O5, a multinuclear manganese cluster, whether mononuclear manganese can also efficiently catalyse water oxidation has been a long-standing question. Herein, we found that a heterogeneous catalyst with mononuclear manganese embedded in nitrogen-doped graphene (Mn-NG) shows a turnover frequency as high as 214 s−1 for chemical water oxidation and an electrochemical overpotential as low as 337 mV at a current density of 10 mA cm−2. Structural characterization and density functional theory calculations reveal that the high activity of Mn-NG can be attributed to the mononuclear manganese ion coordinated with four nitrogen atoms embedded in the graphene matrix.

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Fig. 1: Structural characterizations of Mn-G and Mn-NG.
Fig. 2: Chemical and electrochemical water oxidation properties of Mn-G and Mn-NG.
Fig. 3: Evaluation of catalytic activity by DFT simulations.
Fig. 4: Proposed water oxidation mechanism.

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Data availability

The data that support the findings of this study are available from the corresponding author upon reasonable request.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (No. 21633010), the 973 National Basic Research Program of China (No. 2014CB239403), the Strategic Priority Research Program of Chinese Academy of Sciences (No. XDB17000000) and Honeywell UOP research cooperation (No. 13C0008). Special acknowledgement goes to the assistance of M. Charochak of UOP and J. Wright of IIT for assistance with data collection at MRCAT, and S. Pennycook of NUS for providing the HAADF-STEM device.

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Authors and Affiliations

  1. State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian National Laboratory for Clean Energy, iChEM, Dalian, China

    Jingqi Guan, Fuxiang Zhang, Michel Dupuis, Qinge Huang & Can Li

  2. Department of Chemistry and Institute for Computational and Engineering Sciences, The University of Texas at Austin, Austin, TX, USA

    Zhiyao Duan

  3. Research and Development, Honeywell UOP, Des Plaines, IL, USA

    Shelly D. Kelly & John Qianjun Chen

  4. Shanghai Institute of Applied Physics, Chinese Academy Sciences, Shanghai, China

    Rui Si

  5. Department of Chemical and Biological Engineering and Computation and Data-Enabled Science and Engineering Program, University at Buffalo, State University of New York, Buffalo, NY, USA

    Michel Dupuis

  6. Department of Materials Science and Engineering, National University of Singapore, Singapore, Singapore

    Chunhua Tang

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Contributions

C.L. conceived the project. J.G., F.Z. and J.Q.C. designed the experiments. J.G. performed synthesis, characterization and catalytic reaction experiments. Q.H. performed some catalytic reaction experiments. Z.D. and M.D. performed the DFT calculations. S.D.K. and R.S. measured the XAFS spectra. C.T. measured the HAADF-STEM images of Mn-NG. J.G., C.L. and Z.D. analysed the data and co-wrote the manuscript. All authors discussed the results and commented on the manuscript.

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Correspondence to Can Li.

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Guan, J., Duan, Z., Zhang, F. et al. Water oxidation on a mononuclear manganese heterogeneous catalyst. Nat Catal 1, 870–877 (2018). https://doi.org/10.1038/s41929-018-0158-6

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