Arousing the Reactive Fe Sites in Pyrite (FeS2) via Integration of Electronic Structure Reconfiguration and in Situ Electrochemical Topotactic Transformation for Highly Efficient Oxygen Evolution Reaction

  • Zhi Tan
    Zhi Tan
    Key Laboratory of Cluster Science, Ministry of Education of China, Beijing Key Laboratory of Photoelectronic/Electrophotonic Conversion Materials, School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 100081, P. R. China
    More by Zhi Tan
  • Lekha Sharma
    Lekha Sharma
    Computational Chemistry Laboratory, Department of Chemistry, University of Delhi, Delhi 110007, India
    More by Lekha Sharma
  • Rita Kakkar
    Rita Kakkar
    Computational Chemistry Laboratory, Department of Chemistry, University of Delhi, Delhi 110007, India
    More by Rita Kakkar
  • Tao Meng
    Tao Meng
    Key Laboratory of Cluster Science, Ministry of Education of China, Beijing Key Laboratory of Photoelectronic/Electrophotonic Conversion Materials, School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 100081, P. R. China
    More by Tao Meng
  • Yan Jiang
    Yan Jiang
    Key Laboratory of Cluster Science, Ministry of Education of China, Beijing Key Laboratory of Photoelectronic/Electrophotonic Conversion Materials, School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 100081, P. R. China
    More by Yan Jiang
  • , and 
  • Minhua Cao*
    Minhua Cao
    Key Laboratory of Cluster Science, Ministry of Education of China, Beijing Key Laboratory of Photoelectronic/Electrophotonic Conversion Materials, School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 100081, P. R. China
    *E-mail: [email protected]
    More by Minhua Cao
Cite this: Inorg. Chem. 2019, 58, 11, 7615–7627
Publication Date (Web):May 10, 2019
https://doi.org/10.1021/acs.inorgchem.9b01017
Copyright © 2019 American Chemical Society
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Abstract

Despite significant advances in the development of highly efficient and robust oxygen evolution reaction (OER) electrocatalysts to replace noble-metal catalysts, commercializing OER catalysts with high catalytic activity for sustainable development still remains a great challenge. Especially, transition-metal Fe-based OER catalysts, despite their earth-abundant, cost-efficient, and environmentally benign superiorities over Co- and Ni-based materials, have received relatively insufficient attention because of their poor apparent OER activities. Herein, by rational design, we report Ni-modified pyrite (FeS2) spheres with yolk–shell structure that could serve as pre-electrocatalyst precursors to induce a highly active nickel–iron oxyhydroxide via in situ electrochemical topological transformation under the OER process. Notably, as confirmed by the results of X-ray absorption spectroscopy, X-ray photoelectron spectroscopy, and density functional theory (DFT) calculations, Ni doping could effectively regulate the intrinsic electronic structure of FeS2 to realize a semiconductor-to-semimetal transition, which endows FeS2 with dramatically improved conductivity and water adsorption ability, providing prequisites for subsequent topological transformation. Moreover, systematic post-characterizations further reveal that the optimal Ni-FeS2-0.5 sample completely converts to amorphous Ni-doped FeOOH via an in situ electrochemical transformation with yolk–shell structure well-preserved under the OER conditions. The electronic structure modulation combined with electrochemical topotactic transformation strategies well stimulate the reactive Fe sites in Ni-FeS2-0.5, which show impressively low overpotentials of 250 and 326 mV to drive the current densities (j) of 10 and 100 mA cm–2, respectively, and a Tafel slope as small as 34 mV dec–1 for the OER process. When assembled as a water electrolyzer for the overall water splitting, Ni-FeS2-0.5 can display a low voltage of 1.55 V to drive a current density of 10 mA cm–2, outperforming most of the transition-metal-based bifunctional electrocatalysts to date. This work may provide new insight into the rational design of other high-performance Fe-based OER electrocatalysts and inspire the exploration of cost-effective, ecofriendly electrocatalysts to meet the demand for future sustainable development.

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The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.inorgchem.9b01017.

  • Field-emission SEM images of the Ni-Fe-0.25 precursor, Fe precursor, Ni-FeS2-0.25, and FeS2, TEM images of the Ni-Fe-0.5 precursor, Ni-FeS2-0.25, and FeS2, N2 adsorption–desorption isotherms of Ni-FeS2-0.5, Ni-FeS2-0.25, and FeS2, XRD patterns of the Ni-Fe-0.5 precursor and Ni-FeS2-1, FT-IR spectra of the as-prepared Ni-Fe-0.5 precursor, EDS spectrum of Ni-FeS2-0.5, Fe K-edge k3-weighted EXAFS spectra, Ni K-edge XANES spectra and XAFS k3-weighted oscillation curves, OER polarization curves of NF and Ni-FeS2-0.5 on NF and of Ni-FeS2-0.5 on NF at different scan rates, CV curves of Ni-FeS2-0.5, Ni-FeS2-0.25, and FeS2 at the different scan rates, XPS survey spectra of Ni-FeS2-0.5 before and after OER tests, Raman spectrum and XRD pattern of Ni-FeS2-0.5 after OER tests, and HER polarization curves of NF and Ni-FeS2-0.5 on NF in 1 M KOH (PDF)

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