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Iron-facilitated dynamic active-site generation on spinel CoAl2O4 with self-termination of surface reconstruction for water oxidation

Nature Catalysis volume 2, pages 763–772 (2019)Cite this article

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Abstract

The development of efficient and low-cost electrocatalysts for the oxygen evolution reaction (OER) is critical for improving the efficiency of water electrolysis. Here, we report a strategy using Fe substitution to enable the inactive spinel CoAl2O4 to become highly active and superior to the benchmark IrO2. The Fe substitution is revealed to facilitate surface reconstruction into active Co oxyhydroxides under OER conditions. It also activates deprotonation on the reconstructed oxyhydroxide to induce negatively charged oxygen as an active site, thus significantly enhancing the OER activity of CoAl2O4. Furthermore, it promotes the pre-oxidation of Co and introduces great structural flexibility due to the uplift of the oxygen 2p levels. This results in the accumulation of surface oxygen vacancies along with lattice oxygen oxidation that terminates as Al3+ leaches, preventing further reconstruction. We showcase a promising way to achieve tunable electrochemical reconstruction by optimizing the electronic structure for low-cost and robust spinel oxide OER catalysts.

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Fig. 1: Structural characterizations and OER performances of as-prepared CoFexAl2 − xO4 catalysts.
Fig. 2: In situ investigation of pre-OER behaviours of catalysts and schematic of the surface reconstruction and deprotonation process.
Fig. 3: Electronic interpretation of the effect of Fe substitution on surface reconstruction.
Fig. 4: Reconstruction-terminating mechanism with Al3+ leaching.
Fig. 5: Competitive potential in an electrolyser application.

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The data related to this study are available from the authors upon reasonable request.

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Acknowledgements

T.W., S.S. and J.S. contributed equally to this work. The authors acknowledge support from the Singapore Ministry of Education Tier 2 Grant (MOE2017-T2-1-009) and the Singapore National Research Foundation under its Campus for Research Excellence and Technological Enterprise (CREATE) programme. The authors also thank the Facility for Analysis, Characterisation, Testing and Simulation (FACTS) in Nanyang Technological University for materials characterizations and the XAFCA beamline of the Singapore Synchrotron Light Source for XAFS characterization.

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Author notes

  1. These authors contributed equally: Tianze Wu, Shengnan Sun, Jiajia Song.

Authors and Affiliations

  1. School of Materials Science and Engineering, Nanyang Technological University, Singapore, Singapore

    Tianze Wu, Shengnan Sun, Jiajia Song, Bo Chen, Hanbin Liao, Chee Lip Gan & Zhichuan J. Xu

  2. Solar Fuels Laboratory and Energy Research Institute, Nanyang Technological University, Singapore, Singapore

    Tianze Wu, Shengnan Sun & Zhichuan J. Xu

  3. Institute of Chemical and Engineering Sciences A*STAR, Singapore, Singapore

    Shibo Xi & Yonghua Du

  4. Low Energy Electronic Systems, Singapore-MIT Alliance for Research and Technology, Singapore, Singapore

    Wardhana Aji Sasangka & Chee Lip Gan

  5. Nanyang Environment and Water Research Institute (NEWRI), Interdisciplinary Graduate School (IGS), Nanyang Technological University, Singapore, Singapore

    Hanbin Liao

  6. Department for Management of Science and Technology Development, Ton Duc Thang University, Ho Chi Minh City, Vietnam

    Günther G. Scherer

  7. Faculty of Applied Sciences, Ton Duc Thang University, Ho Chi Minh City, Vietnam

    Günther G. Scherer

  8. Department of Mechanical and Energy Engineering, Southern University of Science and Technology, Shenzhen, Guangdong, China

    Lin Zeng & Haijiang Wang

  9. Department of Materials Science and Engineering, Southern University of Science and Technology, Shenzhen, Guangdong, China

    Hui Li

  10. Chimie du Solide et de l’Energie, UMR 8260, Paris, France

    Alexis Grimaud

  11. Réseau sur le Stockage Electrochimique de l’Energie (RS2E), CNRS FR3459, Amiens, France

    Alexis Grimaud

  12. Energy Research Institute @ Nanyang Technological University, Singapore, Singapore

    Zhichuan J. Xu

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Contributions

T.W., S.S., A.G. and Z.J.X. conceived the original concept and initiated the project. T.W. prepared the materials and performed electrochemical and XRD measurements. S.S. helped design the set-up for in situ XAS measurements. S.X. and T.W. carried out the XAS measurements. Y.D. and T.W. processed and analysed the XAS data. J.S. worked on the DFT calculations and analysis. W.A.S., C.L.G. and B.C. carried out HRTEM and STEM-EELS investigations. L.Z. conducted the measurements in the MEA system. L.Z., H.W., H.Li and G.G.S. analysed the MEA results. T.W. wrote the manuscript with input from all authors, and Z.J.X., A.G. and S.S. revised the manuscript.

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Correspondence to Alexis Grimaud or Zhichuan J. Xu.

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Supplementary Information

Supplementary Figs. 1–18, Supplementary Notes 1–2, Supplementary Tables 1–11 and Supplementary references.

Supplementary Data 1

Atomic coordinates of the optimized computational models.

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Wu, T., Sun, S., Song, J. et al. Iron-facilitated dynamic active-site generation on spinel CoAl2O4 with self-termination of surface reconstruction for water oxidation. Nat Catal 2, 763–772 (2019). https://doi.org/10.1038/s41929-019-0325-4

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