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Lithiation-induced amorphization of Pd3P2S8 for highly efficient hydrogen evolution

Nature Catalysis volume 1, pages 460–468 (2018)Cite this article

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Abstract

Engineering material structures at the atomic level is a promising way to tune the physicochemical properties of materials and optimize their performance in various potential applications. Here, we show that the lithiation-induced amorphization of layered crystalline Pd3P2S8 activates this otherwise electrochemically inert material as a highly efficient hydrogen evolution catalyst. Electrochemical lithiation of the layered Pd3P2S8 crystal results in the formation of amorphous lithium-incorporated palladium phosphosulfide nanodots with abundant vacancies. The structure change during the lithiation-induced amorphization process is investigated in detail. The amorphous lithium-incorporated palladium phosphosulfide nanodots exhibit excellent electrocatalytic activity towards the hydrogen evolution reaction with an onset potential of −52 mV, a Tafel slope of 29 mV dec−1 and outstanding long-term stability. Experimental and theoretical investigations reveal that the tuning of morphology and structure of Pd3P2S8 (for example, dimension decrease, crystallinity loss, vacancy formation and lithium incorporation) contribute to the activation of its intrinsically inert electrocatalytic property. This work provides a unique way for structure tuning of a material to effectively manipulate its catalytic properties and functionalities.

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Fig. 1: Crystal structure of layered Pd3P2S8 and the result of its electrochemical lithiation.
Fig. 2: Analysis of structural changes induced by the electrochemical lithiation process.
Fig. 3: Electrocatalytic activity of Li-PPS NDs in the HER.
Fig. 4: Stability test of Li-PPS NDs in the HER.

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Acknowledgements

This work was supported by MOE under Academic Research Fund Tier 2 (ARC 19/15; numbers MOE2014-T2-2-093, MOE2015-T2-2-057, MOE2016-T2-2-103 and MOE2017-T2-1-162) and Academic Research Fund Tier 1 (2016-T1-001-147, 2016-T1-002-051, 2017-T1-001-150 and 2017-T1-002-119), and NTU under Start-Up Grant M4081296.070.500000 in Singapore. X.W. acknowledges funding support from the NSFC (21421063 and 21573204) and MOST (2016YFA0200602) of China. P. W. would like to acknowledge funding support from the NSFC (11474147) of China. The authors acknowledge the Facility for Analysis, Characterization, Testing and Simulation, Nanyang Technological University, Singapore for use of electron microscopy (and/or X-ray) facilities.

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Author notes

  1. These authors contributed equally: Xiao Zhang, Zhimin Luo, Peng Yu, Yongqing Cai.

Authors and Affiliations

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

    Xiao Zhang, Zhimin Luo, Peng Yu, Chaoliang Tan, Ying Huang, Jian Yang, Ye Chen, Zheng Liu & Hua Zhang

  2. Institute of High Performance Computing, A*STAR, Singapore, Singapore

    Yongqing Cai

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

    Yonghua Du & Armando Borgna

  4. Hefei National Laboratory of Physical Sciences at the Microscale, National Synchrotron Radiation Laboratory, CAS Center for Excellence in Nanoscience, University of Science and Technology of China, Hefei, China

    Daoxiong Wu, Shuangming Chen, Li Song & Xiaojun Wu

  5. National Laboratory of Solid State Microstructures, College of Engineering and Applied Sciences and Collaborative Innovation Center of Advanced Microstructures, Nanjing University, Nanjing, China

    Si Gao & Peng Wang

  6. School of Mechanical and Aerospace Engineering, Nanyang Technological University, Singapore, Singapore

    Zhong Li

  7. Centre for Ion Beam Applications, Department of Physics, Faculty of Science, National University of Singapore, Singapore, Singapore

    Minqin Ren & Thomas Osipowicz

  8. Shanghai Synchrotron Radiation Facility, Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai, China

    Zheng Jiang & Jiong Li

  9. Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore, Singapore

    Chung Yen Ang & Yanli Zhao

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Contributions

H.Z. proposed the research direction and guided the project. X.Z. designed and performed the experiments. Z.Luo carried out the electrochemical experiments. P.Y. and Z.Liu grew the Pd3P2S8 crystal. Y.Cai, D.W. and X.W. performed the theoretical work. Y.D., Z.J., J.L. and A.B. performed the XAS characterization, and Y.D., S.C. and L.S. assisted in the data fitting and analysis. S.G and P.W. carried out the NBED measurement. Z.Li conducted the XPS measurement. Y.H. performed the AFM characterization. C.Y.A. and Y.Z. conducted the single-crystal diffraction characterization. M.R. and T.O. performed the NRA characterization. C.T., J.Y. and Y.Chen performed supporting experiments. X.Z. and H.Z. analysed and discussed all experimental results and drafted the manuscript. All authors checked the manuscript and agreed with the content.

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Correspondence to Hua Zhang.

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Supplementary information

Supplementary Information

Supplementary Figures 1–34, Supplementary Tables 1–10, Supplementary Notes 1–14, Supplementary References

Crystallographic data

Crystallographic data for Pd3P2S8, CCDC reference 1832692

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Zhang, X., Luo, Z., Yu, P. et al. Lithiation-induced amorphization of Pd3P2S8 for highly efficient hydrogen evolution. Nat Catal 1, 460–468 (2018). https://doi.org/10.1038/s41929-018-0072-y

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