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Spatially strain-induced and selective preparation of MoxN (x = 1, 2) as a highly effective nanoarchitectonic catalyst for hydrogen evolution reaction in a wide pH range

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Developing highly efficient catalysts for the hydrogen evolution reaction (HER) is crucial to commercial water splitting in the global efforts to mitigate fossil fuel combustion and combat global climate change. Molybdenum nitrides (MoxN) such as γ-Mo2N and δ-MoN are promising HER catalysts. Although δ-MoN has better HER characteristics, controllable preparation of the materials is still challenging. Herein, selective preparation of γ-Mo2N and δ-MoN is demonstrated by controlling the spatial stress. The hybrid δ-MoN and N-doped carbon composite (MoN/NC) consists of MoN layers and 1-nm-thick carbon layers. The carbon layers polarized by the high valence state of Mo in MoN provide the adsorption sites for H+, and the NC layers also facilitate electron transport during the catalytic process. As a result, MoN/NC exhibits remarkable HER activity such as low overpotentials of 93, 211 and 141 mV to attain a current density of 10 mA·cm−2 as well as small Tafel slopes of 44.5, 83.2 and 65.4 mV·dec−1 in acidic, neutral and basic electrolytes of 0.5 mol·L−1 H2SO4, 1 mol·L−1 PBS, and 1 mol·L−1 KOH, respectively. The spatial stress effects enable selective preparation of specific phases in catalysts, and the pertinent mechanism provides important guidance to the preparation and optimization of advanced catalysts.

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摘要

发展高性能电解水析氢催化剂是十分重要的, 它可以缓解人们对石油等化石能源的依赖和减轻气候变暖等问题。在氮化钼一类材料（MoxN）中, MoN和Mo2N是十分重要的析氢催化剂。 尽管MoN具有更好催化活性, 但是它的可控制备依旧是一个挑战。本文中, 我们首次提出了通过压应力作用来选择性制备MoN和Mo2N。 通常直接退火处理MoO3, 只能得到Mo2N。若先将十二胺分子DDA插入MoO3原子层间, 再经过后续退火处理, 利用材料间的压应力, 便可以直接得到MoN相, 而不是Mo2N相。 同时层间的DDA直接转变成为N参杂的C层, 具有良好的导电性和化学稳定性。 因此, MoN/NC表现出来非常好的析氢性能, 如分别在酸性, 中性和碱性溶液中, 在较低的过电势93, 211 和141 mV达到10 mA·cm−2的电流密度。 这种应用空间应力的方式可以直接选择性制备想要得到的产物, 可以为其他催化剂的制备和合成提供有效的帮助。

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Acknowledgments

This study was financially supported by Hong Kong Scholars Program (No. XJ2018009), City University of Hong Kong Strategic Research Grant (SRG) (No. 7005505), City University of Hong Kong Donation Research Grant (No. 9229021), the National Natural Science Foundation of China (No. 52003129), Shandong Provincial Natural Science Foundation, China (No. ZR2019BB006) and State Key Laboratory of Powder Metallurgy, Central South University, Changsha, China.

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Authors and Affiliations

  1. Department of Physics, Department of Materials Science and Engineering, City University of Hong Kong, Hong Kong, 999077, China

    Chao Huang, Xiao-Lin Zhang, Jing Tang, Dan Li, Qing-Dong Ruan, Liang-Liang Liu, Fang-Yu Xiong, Bin Wang, Yue Xu, Sui-Han Cui, Yang Luo, Qing-Wei Li & Paul K. Chu

  2. Department of Biomedical Engineering, City University of Hong Kong, Hong Kong, 999077, China

    Chao Huang, Xiao-Lin Zhang, Jing Tang, Dan Li, Qing-Dong Ruan, Liang-Liang Liu, Fang-Yu Xiong, Bin Wang, Yue Xu, Sui-Han Cui, Yang Luo, Qing-Wei Li & Paul K. Chu

  3. State Key Laboratory of Powder Metallurgy, Central South University, Changsha, 410011, China

    Chao Huang

  4. School of Mechanical Engineering, Liaoning Petrochemical University, Fushun, 113001, China

    Jing Tang

  5. Advanced Research Institute for Multidisciplinary Science, Qilu University of Technology (Shandong Academy of Sciences), Jinan, 250307, China

    Qing-Wei Li

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  1. Chao Huang
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Huang, C., Zhang, XL., Tang, J. et al. Spatially strain-induced and selective preparation of MoxN (x = 1, 2) as a highly effective nanoarchitectonic catalyst for hydrogen evolution reaction in a wide pH range. Rare Met. 42, 1446–1452 (2023). https://doi.org/10.1007/s12598-022-02227-3

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