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SCIENCE CHINA Materials, Volume 62, Issue 9: 1285-1296(2019) https://doi.org/10.1007/s40843-019-9434-7

In situ construction of surface defects of carbon-doped ternary cobalt-nickel-iron phosphide nanocubes for efficient overall water splitting

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  • ReceivedFeb 23, 2019
  • AcceptedApr 28, 2019
  • PublishedMay 23, 2019

Abstract

The ternary cobalt–nickel–iron phosphide nanocubes (P-Co0.9Ni0.9Fe1.2 NCs) with high intrinsic activity, conductivity, defect concentration and optimized ratio have been realized through a facile phosphorization treatment using ternary cobalt-nickel-iron nanocubes of Prussian blue analogs (PBA) as a precursor. The scanning electron microscopy and transmission electron microscopy results show that the P-Co0.9Ni0.9Fe1.2 NCs maintain a cubic structure with a rough surface, implying the rich surface defects as exposed active sites. The thermal phosphorization of the ternary PBA precursor not only provids carbon doping but also leads to the in situ construction of surface defects on the NCs. The carbon doping from the PBA precursor lowers the charge transfer resistance and optimizes the electronic transformation. The synergistic effect among the ternary metal ions and rich defects contributes to the enhanced electrocatalytic performance. The P-Co0.9Ni0.9Fe1.2 NCs achieve low overpotentials of −200.7 and 273.1 mV at a current density of 10 mA cm−2 for the hydrogen evolution reaction and the oxygen evolution reaction, respectively. The potential of overall water splitting reaches 1.52 V at a current density of 10 mA cm−2. The long-term stability of the electrocatalysts was also evaluated. This work provides a facile method to design efficient transition-metal-based bifunctional electrocatalysts for overall water splitting.


Funded by

Natural Science Foundation of Shandong Province(ZR2017MB059)

the Major Program of Shandong Province Natural Science Foundation(ZR2018ZC0639)

the National Natural Science Foundation of China(21776314)

the Fundamental Research Funds for the Central Universities(18CX05016A)

and the Postgraduate Innovation Project of China University of Petroleum(YCX2018074)


Acknowledgment

This work was supported by the Natural Science Foundation of Shandong Province (ZR2017MB059), the Major Program of Shandong Province Natural Science Foundation (ZR2018ZC0639), the National Natural Science Foundation of China (21776314), the Fundamental Research Funds for the Central Universities (18CX05016A), and the Postgraduate Innovation Project of China University of Petroleum (YCX2018074).


Interest statement

The authors declare no conflict of interest.


Contributions statement

All authors contributed to the discussion and preparation of the manuscript. The final version of the manuscript was approved by all authors.


Author information

Wenkun Gao is currently a master candidate under the supervision of Professor Bin Dong in the State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China). He received his bachelor's degree majored in engineering from Jining University in 2015. His research interest focuses on electrochemical and photoelectrochemical water splitting.


Bin Dong received PhD degree from Lanzhou University in 2008. He was a visiting scholar in Marquette University from 2014 to 2015. Now he is an associate professor in the College of Science, China University of Petroleum (East China). His research interests focus on the design and synthesis of functional materials for energy conversion and storage, such as electrocatalysis and photoelectrocatalysis for water splitting.


Supplement

Supplementary information

Supporting data are available in the online version of this paper.


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  • Figure 1

    XRD patterns: (a) Ni1.8Fe1.2 NCs, Co1.8Fe1.2 NCs, Co0.9Ni0.9Fe1.2 NCs, Co1.2Ni0.6Fe1.2 NCs, and Co0.6Ni1.2Fe1.2 NCs; (b) P-Ni1.8Fe1.2 NCs, P-Co1.8Fe1.2 NCs, P-Co0.9Ni0.9Fe1.2 NCs, P-Co1.2Ni0.6Fe1.2 NCs, and P-Co0.6Ni1.2Fe1.2 NCs.

  • Scheme 1

    Schematic of consecutive processes for synthesizing ternary metal phosphides of P-Co0.9Ni0.9Fe1.2 NCs.

  • Figure 2

    XPS spectra of the P-Co0.9Ni0.9Fe1.2 NCs: (a) survey; (b) Fe 2p; (c) Co 2p; (d) Ni 2p; (e) P 2p; and (f) C 1s.

  • Figure 3

    SEM images: (a–c) Co0.9Ni0.9Fe1.2 NCs and (d–f) P-Co0.9Ni0.9Fe1.2 NCs.

  • Figure 4

    (a–c) HRTEM images, (d) SEM mapping image, and (e) EDX spectra of P-Co0.9Ni0.9Fe1.2 NCs.

  • Figure 5

    HER electrochemical performances of the P-Ni1.8Fe1.2 NCs, P-Co1.8Fe1.2 NCs, P-Co0.9Ni0.9Fe1.2 NCs, P-Co1.2Ni0.6Fe1.2 NCs, and the P-Co0.6Ni1.2Fe1.2 NCs in 1 mol L−1 KOH: (a) LSVs; (b) Tafel plots; (c) Nyquist plots; and (d) the determined double-layer capacitance (Cdl) values.

  • Figure 6

    OER electrochemical performances of the P-Ni1.8Fe1.2 NCs, P-Co1.8Fe1.2 NCs, P-Co0.9Ni0.9Fe1.2 NCs, P-Co1.2Ni0.6Fe1.2 NCs, and P-Co0.6Ni1.2Fe1.2 NCs in 1.0 mol L−1 KOH. (a) LSVs; (b) Tafel plots; (c) Nyquist plots; and (d) the determined double-layer capacitance (Cdl).

  • Figure 7

    (a) Polarization curves in 1.0 mol L−1 KOH for electrocatalysts whose anode and cathode both contain P-Co0.9Ni0.9Fe1.2 NCs. (b) The current density as a function of time at a potential of 1.52 V (vs. RHE).

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