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Journal of Advanced Ceramics 2022, 11(8): 1294-1306 https://doi.org/10.1007/s40145-022-0610-6
Research Article | Open Access | Issue | Published: 18 July 2022

Experimental and DFT studies of flower-like Ni-doped Mo2C on carbon fiber paper: A highly efficient and robust HER electrocatalyst modulated by Ni(NO3)2 concentration

Show Author's Information Lei ZHANGa,†,  Zhihui HUa,†,  Juntong HUANGa ( ),  Zhi CHENa,  Xibao LIa,  Zhijun FENGa,  Huiyong YANGa,  Saifang HUANGb( ),  Ruiying LUOa,c( )
School of Materials Science and Engineering, Nanchang Hangkong University, Nanchang 330063, China
School of Materials Science and Engineering, Jiangsu University of Science and Technology, Zhenjiang 212003, China
Research Institute for Frontier Science, Beihang University, Beijing 100191, China

† Lei Zhang and Zhihui Hu contributed equally to this work.

Keywords:
water splitting, hydrogen evolution reaction (HER), Mo2C@CFP electrocatalyst, nickel (Ni) doping, molten salt method
Cite this article:
ZHANG L, HU Z, HUANG J, et al. Experimental and DFT studies of flower-like Ni-doped Mo2C on carbon fiber paper: A highly efficient and robust HER electrocatalyst modulated by Ni(NO3)2 concentration. Journal of Advanced Ceramics, 2022, 11(8): 1294-1306. https://doi.org/10.1007/s40145-022-0610-6
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Abstract Full text Electronic supplementary material About this article

Developing highly efficient and stable non-precious metal catalysts for water splitting is urgently required. In this work, we report a facile one-step molten salt method for the preparation of self-supporting Ni-doped Mo2C on carbon fiber paper (Ni-Mo2CCB/CFP) for hydrogen evolution reaction (HER). The effects of nickel nitrate concentration on the phase composition, morphology, and electrocatalytic HER performance of Ni-doped Mo2C@CFP electrocatalysts was investigated. With the continuous increase of Ni(NO3)2 concentration, the morphology of Mo2C gradually changes from granular to flower-like, providing larger specific surface area and more active sites. Doping nickel (Ni) into the crystal lattice of Mo2C largely reduces the impedance of the electrocatalysts and enhances their electrocatalytic activity. The as-developed Mo2C-3 M Ni(NO3)2/CFP electrocatalyst exhibits high catalytic activity with a small overpotential of 56 mV at a current density of 10 mA·cm-2. This catalyst has a fast HER kinetics, as demonstrated by a very small Tafel slope of 27.4 mV·dec-1, and persistent long-term stability. A further higher Ni concentration had an adverse effect on the electrocatalytic performance. Density functional theory (DFT) calculations further verified the experimental results. Ni doping could reduce the binding energy of Mo-H, facilitating the desorption of the adsorbed hydrogen (Hads) on the surface, thereby improving the intrinsic catalytic activity of Ni-doped Mo2C-based catalysts. Nevertheless, excessive Ni doping would inhibit the catalytic activity of the electrocatalysts. This work not only provides a simple strategy for the facile preparation of non-precious metal electrocatalysts with high catalytic activity, but also unveils the influence mechanism of the Ni doping concentration on the HER performance of the electrocatalysts from the theoretical perspective.


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Electronic supplementary material
About this article

Experimental and DFT studies of flower-like Ni-doped Mo2C on carbon fiber paper: A highly efficient and robust HER electrocatalyst modulated by Ni(NO3)2 concentration

Show Author's information Lei ZHANGa,†, Zhihui HUa,†, Juntong HUANGa ( ), Zhi CHENa, Xibao LIa, Zhijun FENGa, Huiyong YANGa, Saifang HUANGb( ), Ruiying LUOa,c( )
School of Materials Science and Engineering, Nanchang Hangkong University, Nanchang 330063, China
School of Materials Science and Engineering, Jiangsu University of Science and Technology, Zhenjiang 212003, China
Research Institute for Frontier Science, Beihang University, Beijing 100191, China

† Lei Zhang and Zhihui Hu contributed equally to this work.

Abstract

Developing highly efficient and stable non-precious metal catalysts for water splitting is urgently required. In this work, we report a facile one-step molten salt method for the preparation of self-supporting Ni-doped Mo2C on carbon fiber paper (Ni-Mo2CCB/CFP) for hydrogen evolution reaction (HER). The effects of nickel nitrate concentration on the phase composition, morphology, and electrocatalytic HER performance of Ni-doped Mo2C@CFP electrocatalysts was investigated. With the continuous increase of Ni(NO3)2 concentration, the morphology of Mo2C gradually changes from granular to flower-like, providing larger specific surface area and more active sites. Doping nickel (Ni) into the crystal lattice of Mo2C largely reduces the impedance of the electrocatalysts and enhances their electrocatalytic activity. The as-developed Mo2C-3 M Ni(NO3)2/CFP electrocatalyst exhibits high catalytic activity with a small overpotential of 56 mV at a current density of 10 mA·cm-2. This catalyst has a fast HER kinetics, as demonstrated by a very small Tafel slope of 27.4 mV·dec-1, and persistent long-term stability. A further higher Ni concentration had an adverse effect on the electrocatalytic performance. Density functional theory (DFT) calculations further verified the experimental results. Ni doping could reduce the binding energy of Mo-H, facilitating the desorption of the adsorbed hydrogen (Hads) on the surface, thereby improving the intrinsic catalytic activity of Ni-doped Mo2C-based catalysts. Nevertheless, excessive Ni doping would inhibit the catalytic activity of the electrocatalysts. This work not only provides a simple strategy for the facile preparation of non-precious metal electrocatalysts with high catalytic activity, but also unveils the influence mechanism of the Ni doping concentration on the HER performance of the electrocatalysts from the theoretical perspective.

Keywords: water splitting, hydrogen evolution reaction (HER), Mo2C@CFP electrocatalyst, nickel (Ni) doping, molten salt method

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Publication history

Received: 11 January 2022
Revised: 03 May 2022
Accepted: 07 May 2022
Published: 18 July 2022
Issue date: August 2022

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© The Author(s) 2022.

Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (Grant Nos. 51862024, 51772140, and 51962023) and Key Research and Development Program of Jiangxi Province (Grant No. 20203BBE53066).

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