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Engineering the electronic structure of single atom Ru sites via compressive strain boosts acidic water oxidation electrocatalysis

Nature Catalysis volume 2, pages 304–313 (2019)Cite this article

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Abstract

Single-atom precious metal catalysts hold the promise of perfect atom utilization, yet control of their activity and stability remains challenging. Here we show that engineering the electronic structure of atomically dispersed Ru1 on metal supports via compressive strain boosts the kinetically sluggish electrocatalytic oxygen evolution reaction (OER), and mitigates the degradation of Ru-based electrocatalysts in an acidic electrolyte. We construct a series of alloy-supported Ru1 using different PtCu alloys through sequential acid etching and electrochemical leaching, and find a volcano relation between OER activity and the lattice constant of the PtCu alloys. Our best catalyst, Ru1–Pt3Cu, delivers 90 mV lower overpotential to reach a current density of 10 mA cm−2, and an order of magnitude longer lifetime over that of commercial RuO2. Density functional theory investigations reveal that the compressive strain of the Ptskin shell engineers the electronic structure of the Ru1, allowing optimized binding of oxygen species and better resistance to over-oxidation and dissolution.

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Fig. 1: Characterizations of Cu@Ru1–PtCu3, Ru1–PtCu and Ru1–Pt3Cu.
Fig. 2: Fine-structure characterizations of Ru1–Pt3Cu.
Fig. 3: Activity and stability investigations of Ru1–Pt3Cu during the OER process.
Fig. 4: Overpotential and electronic structure on Ru1–PtxCu4–x(111) with pre-adsorbed oxygen.

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The data that support the plots within this paper and other 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 Key R&D Program of China (2017YFA0208300, 2017YFA0700104, 2017YFB0602205 and 2018YFA0208603), the National Natural Science Foundation of China (21522107, 21671180, 91645202, 91421315, 21521091, 21390393 and U1463202) and the Chinese Academy of Sciences (QYZDJ-SSW-SLH054). The authors acknowledge funding support from CAS Fujian Institute of Innovation, and thank the photoemission endstations BL1W1B in the Beijing Synchrotron Radiation Facility (BSRF), BL14W1 in the Shanghai Synchrotron Radiation Facility (SSRF) and BL10B and BL11U in the National Synchrotron Radiation Laboratory (NSRL) for help with characterizations.

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Author notes

  1. These authors contributed equally: Yancai Yao, Sulei Hu, Wenxing Chen.

Authors and Affiliations

  1. School of Chemistry and Materials Science, iChEM, CAS Center for Excellence in Nanoscience, University of Science and Technology of China, Hefei National Laboratory for Physical Sciences at the Microscale, Hefei, China

    Yancai Yao, Sulei Hu, Weichen Wei, Xiaoqian Wang, Geng Wu, Baiquan Zhu, Wei Liu, Zhijun Li, Dongsheng He, Zhenggang Xue, Yanxia Chen, Xun Hong, Wei-Xue Li & Yuen Wu

  2. Department of Chemistry, Tsinghua University, Beijing, China

    Wenxing Chen & Yadong Li

  3. Institute of Industrial Catalysis, School of Chemical Engineering and Technology, Xi’an Jiaotong University, Xi’an, China

    Zheng-Qing Huang & Chun-Ran Chang

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

    Tao Yao, Xusheng Zheng & Shiqiang Wei

  5. Center for Electron Microscopy TUT-FEI Joint Laboratory Institute for New Energy Materials & Low-Carbon Technologies School of Materials Science and Engineering, Tianjin University of Technology, Tianjin, China

    Ruirui Liu, Ketao Zang, Wenjuan Yuan & Jun Luo

  6. NEST Lab, Department of chemistry, College of Science, Shanghai University, Shanghai, China

    Tongwei Yuan

  7. Shanghai Synchrotron Radiation Facilities, Shanghai Institute of Applied Physics, Chinese Academy of Science, Shanghai, China

    Yu Wang

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

    Juncai Dong

  9. Department of Chemistry, Technical University Berlin, Berlin, Germany

    Peter Strasser

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  1. Yancai Yao
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Contributions

Y.W. and Y.L. designed the study. Y.Y., X.W., G.W. and W.W. carried out the sample synthesis and electrochemical measurements. K.Z., R.L., W.Y., D.H. and J.L. performed the electron-microscopy characterization. S.H., W.L., Z.H. and C.R. finished the DFT calculations and analysis. W.C., Y.W. and J.D. carried out the in situ and ex situ X-ray absorption fine structure and analysis. Y.C. and B.Z. performed the in situ infrared experiment. Y.W., Y.Y., S.H. and W.L. wrote the manuscript. The other authors provided reagents and performed some of the experiments. P.S. reviewed the data and revised portions of the manuscript, triggering helpful discussions.

Corresponding authors

Correspondence to Wei-Xue Li or Yuen Wu.

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Supplementary information

Supplementary Information

Supplementary Figures 1–33, Supplementary Tables 1–9, Supplementary Notes 1-7 and Supplementary References.

Supplementary Data 1

Atomic coordinates of the optimized models.

Supplementary Video 1

Animated voxel recording the tomogram rotation of Cu@Ru1–PtCu3.

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Yao, Y., Hu, S., Chen, W. et al. Engineering the electronic structure of single atom Ru sites via compressive strain boosts acidic water oxidation electrocatalysis. Nat Catal 2, 304–313 (2019). https://doi.org/10.1038/s41929-019-0246-2

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