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Bimetallic nickel-molybdenum/tungsten nanoalloys for high-efficiency overall hydrazine splitting in seawater electrolytes

用于海水电解质中高效分解水合肼的镍-钼/钨双金属纳米合金

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Abstract

Replacing sluggish oxygen evolution reaction (OER) by hydrazine oxidation reaction (HzOR) is a promising way to produce hydrogen and suppress unfavorable chlorine evolution reaction (ClER) in long-term seawater splitting. However, few catalysts can meet the demand to process outstanding hydrogen evolution reaction (HER) and HzOR simultaneously to achieve relatively low cell voltage in a two-electrode system. Herein, we report bimetallic Ni4Mo/Ni4W nanoalloys as bifunctional catalysts with remarkable catalytic activity towards both HER (−7 mV at 10 mA cm−2) and HzOR (−16 mV at 10 mA cm−2). Surprisingly, low cell voltages of 34, 295 and 548 mV are required to achieve 10, 100 and 200 mA cm−2 in a two-electrode system with ideal stability in 1.0 mol L−1 KOH/2.0 mol L−1 NaCl/0.1 mol L−1 N2H4 electrolyte. Density functional theory calculations disclose that the Ni−Mo/W coupling can not only reduce the free energy of water dissociation as well as hydrogen adsorption/desorption, but also optimize the dehydrogenation kinetics of adsorbed intermediates.

摘要

利用水合肼氧化反应(HzOR)取代缓慢的析氧反应(OER)是一种可以在海水裂解中长期产生氢气并抑制不利的析氯反应(ClER)的方法. 然而, 很少有催化剂能够满足在双电极系统中同时呈现出优异的析氢反应(HER)和HzOR以达到较低的电池电压的要求. 在此, 我们报道了双金属Ni4Mo/Ni4W纳米合金作为双功能催化剂, 该催化剂对HER(−7 mV, 10 mA cm−2)和HzOR (−16 mV, 10 mA cm−2)具有显著的催化活性. 在1.0 mol L−1 KOH/2.0 mol L−1 NaCl/0.1 mol L−1 N2H4电解液中, 双电极系统需要34, 295和548 mV的低电池电压就能达到10, 100和200 mA cm−2. 密度泛函理论计算表明, Ni−Mo/W耦合不仅可以降低水解离的自由能和氢的吸附/脱附, 而且可以优化吸附水合肼中间体的脱氢动力学.

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Acknowledgements

This work was supported by the National Key R&D Program of China (2021YFB3801301) and the National Natural Science Foundation of China (22075076, 22005098 and 22208092).

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Authors and Affiliations

  1. State Key Laboratory of Chemical Engineering, School of Chemical Engineering, East China University of Science and Technology, Shanghai, 200237, China

    Keyu Wang  (王珂宇), Chen Liang  (梁晨), Zhiyuan Yi  (易致远), Fang Xu  (徐放), Yixing Wang  (王一兴), Linfeng Lei  (雷林峰), Linzhou Zhuang  (庄林洲) & Zhi Xu  (徐至)

Authors
  1. Keyu Wang  (王珂宇)
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  2. Chen Liang  (梁晨)
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  3. Zhiyuan Yi  (易致远)
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  4. Fang Xu  (徐放)
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  5. Yixing Wang  (王一兴)
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  6. Linfeng Lei  (雷林峰)
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  7. Linzhou Zhuang  (庄林洲)
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  8. Zhi Xu  (徐至)
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Contributions

Author contributions Xu Z and Zhuang L conceived this research. Wang K and Zhuang L wrote the manuscript with support from Lei L. Wang K and Liang C carried out the experiments. Wang K, Liang C and Yi Z carried out the material characterization. Wang K and Xu F performed the theoretical calculations. Wang Y assisted with the material characterization. All authors discussed the results and commented on the manuscript.

Corresponding authors

Correspondence to Linzhou Zhuang  (庄林洲) or Zhi Xu  (徐至).

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Conflict of interest The authors declare that they have no conflict of interest.

Additional information

Keyu Wang is currently a PhD candidate in chemical engineering under the supervision of Profs Zhi Xu and Linzhou Zhuang at the East China University of Science and Technology (ECUST). His research focuses on the rational design and synthesis of novel electrocatalysts for water splitting.

Zhi Xu received his PhD degree from the University of Cincinnati, USA in 2015. He did his postdoctoral research at the University of Cincinnati and the University of Oxford from 2015 to 2019. He joined ECUST and was promoted to a full professor in 2019. His research interests include the preparation and mechanism study of ion-conducting membrane with regular pore structure, the synthesis and application of gas separation membranes, and efficient catalysts for electrocatalytic and thermocatalytic hydrogen production.

Linzhou Zhuang is currently an associate professor at ECUST. He received his BSc and MSc degrees from the School of Chemistry and Chemical Engineering, Sun Yatsen University in 2012 and 2014, respectively. He received his PhD degree from the School of Chemical Engineering, University of Queensland, Australia in 2019, and then joined ECUST as an associate researcher. His research interests focus on the design and synthesis of highly efficient catalysts and electrolysers for freshwater and seawater splitting.

Supplementary information Experimental details and supporting data are available in the online version of the paper.

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40843_2023_2553_MOESM1_ESM.pdf

Bimetallic nickel-molybdenum/tungsten nanoalloys for high-efficiency overall hydrazine splitting in seawater electrolytes

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Wang, K., Liang, C., Yi, Z. et al. Bimetallic nickel-molybdenum/tungsten nanoalloys for high-efficiency overall hydrazine splitting in seawater electrolytes. Sci. China Mater. 66, 3846–3854 (2023). https://doi.org/10.1007/s40843-023-2553-7

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