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无机材料学报

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P,Se共掺杂NiMoO4双功能催化剂的制备及其电解海水性能研究

于雷, 何承添, 于静, 王君   

  1. 哈尔滨工程大学 材料科学与化学工程学院,哈尔滨 150001
  • 收稿日期:2026-06-29 修回日期:2026-09-27
  • 通讯作者: 于 静, 副教授. E-mail: jing.yu@hrbeu.edu.cn
  • 作者简介:于 雷(1988–), 男, 博士研究生. E-mail: yulei880716@163.com
  • 基金资助:
    中央高校基本科研业务费项目(3072025YC1007)

Preparation of P,Se-doped NiMoO4 Bifunctional Catalysts and Their Seawater Electrolysis Performance

YU Lei, HE Chengtian, YU Jing, WANG Jun   

  1. College of Materials Science and Chemical Engineering, Harbin Engineering University, Harbin 150001, China
  • Received:2026-06-29 Revised:2026-09-27
  • Contact: YU Jing, associate professor. E-mail: jing.yu@hrbeu.edu.cn
  • About author:YU Lei (1988–), male, PhD candidate. E-mail: yulei880716@163.com
  • Supported by:
    Fundamental Research Funds of the Central University (3072025YC1007) 

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摘要： 海水电解制氢是实现能源结构低碳化转型的重要途径,但海水的离子环境复杂,尤其是氯离子的腐蚀与催化位点毒化效应,严重制约电极催化剂的活性与长期稳定性。因此开发高效耐蚀的双功能电极催化剂,成为当前的研究重点。本研究采用一步水热法结合低温磷硒掺杂工艺,制备了P和Se共掺杂的NiMoO4双功能催化剂(P,Se-NiMoO4)。对材料的物相结构与微观形貌进行了系统表征,结果表明,P与Se掺杂并未破坏NiMoO4的棒状微观结构,同时诱导了表面纳米颗粒的原位生成,显著增加了材料的电化学活性表面积与表面粗糙度。该催化剂在碱水及真实海水中均表现出优异的双功能催化活性与稳定性。在1 mol/L KOH碱性电解液中,其析氢反应过电位仅为169.1 mV(@ 100 mA·cm–2),析氧反应过电位为319.9 mV(@100 mA·cm–2)。在真实海水体系中,该催化剂仍能保持优良的性能和高选择性,并展现出长达100 h的卓越稳定性。P与Se共同掺杂有效调控了NiMoO4的电子结构,加速了界面电荷传输动力学。此外,富电子的掺杂位点通过静电排斥作用有效抑制了氯离子的吸附与侵蚀,显著提升了材料的耐腐蚀性能。本研究为开发高性能、低成本的海水电解催化剂提供了新的设计思路与实验依据。

关键词: 电解海水, 双功能催化剂, P,Se共掺杂, NiMoO4

Abstract: Seawater electrolysis for hydrogen production represents a critical pathway to advance the low-carbon transition of the energy structure. However, the complex ionic environment of seawater, especially the corrosion effect and catalytic active site poisoning effect induced by chloride ions, severely restricts the catalytic activity and long-term operational stability of electrode catalysts. Accordingly, developing high-efficiency and corrosion-resistant bifunctional electrode catalysts has become a core research focus in this field. A P, Se co-doped NiMoO4 bifunctional electrocatalyst (P,Se-NiMoO4) was fabricated via a one-step hydrothermal method combined with a low-temperature phosphorus-selenium doping strategy. Incorporation of P and Se dopants does not damage the rod-like microstructure of NiMoO4. Meanwhile, in-situ generation of surface nanoparticles is induced, which substantially enlarges the electrochemical active surface area and surface roughness of the catalyst. The obtained catalyst delivers outstanding bifunctional catalytic activity and durability in both alkaline freshwater and natural seawater electrolytes. In 1 mol·L–1 KOH alkaline solution, the hydrogen evolution reaction (HER) overpotential is merely 169.1 mV at a current density of 100 mA cm–2, and the oxygen evolution reaction (OER) overpotential reaches 319.9 mV at 100 mA cm–2. When applied to natural seawater electrolysis, the catalyst retains high catalytic efficiency and favorable Faradaic selectivity, along with remarkable long-term stability over 100 h continuous operation. The co-doping of P and Se effectively modulates the electronic configuration of NiMoO4 and accelerates the interfacial charge transfer kinetics. Furthermore, the electron-rich doping sites suppress the adsorption and corrosion of chloride ions through electrostatic repulsion, greatly strengthening the anti-corrosion capability of the catalyst. This research offers innovative design strategies and experimental foundations for low-cost electrocatalysts with high performance toward seawater electrolysis.

Key words: seawater electrolysis, bifunctional catalyst, P and Se co-doped, NiMoO4

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