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Issue 20, 2019
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A highly efficient alkaline HER Co–Mo bimetallic carbide catalyst with an optimized Mo d-orbital electronic state

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Abstract

Efficient catalysts for the alkaline hydrogen evolution reaction are continuously pursued to accelerate the kinetics of water splitting and enhance the conversion of renewable energy to chemical feedstock. Among numerous candidates, noble-metal-free Mo2C catalysts are favored because of their low cost, abundance and similar d-orbital electronic state to the state of the art platinum. However, due to the high empty d-orbital density of high-valence Mo species in Mo2C, the HER performance was impaired. We reason that introducing modulators into the Mo2C framework that could decrease the empty d-orbital density and valence states of Mo may be an efficient way to optimize the HER energetics. Herein, inspired by the versatile electronic structures of 3d metals, we carried out first principles calculations using 3d metal Co as a dopant of Mo2C to construct Co–Mo bimetallic carbide and found an enhanced HER activity after Co incorporation. We further synthesized a Co–Mo bimetallic carbide catalyst. The obtained catalysts achieved excellent alkaline HER performance with the lowest overpotential of −46 mV at −10 mA cm−2, a low Tafel slope of 46 mV dec−1 and great stability without any decay after a 500 hour reaction. The X-ray adsorption spectroscopy study showed that the valence state of Mo was decreased by the Co dopant and we propose that the decrease of Mo valence states should be the reason for the better HER performance of the bimetallic carbide than bulk Mo2C.

Graphical abstract: A highly efficient alkaline HER Co–Mo bimetallic carbide catalyst with an optimized Mo d-orbital electronic state

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Publication details

The article was received on 17 Mar 2019, accepted on 28 Apr 2019 and first published on 29 Apr 2019


Article type: Communication
DOI: 10.1039/C9TA02886B
J. Mater. Chem. A, 2019,7, 12434-12439

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    A highly efficient alkaline HER Co–Mo bimetallic carbide catalyst with an optimized Mo d-orbital electronic state

    G. Liu, H. Bai, Y. Ji, L. Wang, Y. Wen, H. Lin, L. Zheng, Y. Li, B. Zhang and H. Peng, J. Mater. Chem. A, 2019, 7, 12434
    DOI: 10.1039/C9TA02886B

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