催化学报

催化学报 ›› 2026, Vol. 89: 218-231.DOI: 10.1016/S1872-2067(26)65162-5

• 论文 • 上一篇    下一篇

三维碳泡沫与阴离子空位协同调控镍铁双金属硫化物用于高效碱性/海水电解析氢反应

张莹a,1, 范增源a,1, 章小洪a, 赵波a, 王艺凝a,*(), 吴云鹏a,b,*(), Hiang Kwee Leec, 王佳伟a,b,*()   

  1. a长春理工大学化学与环境工程学院,吉林省光功能材料与化学科技创新中心, 吉林省光功能材料与化学国际联合研究中心,吉林长春 130022,中国
    b长春理工大学重庆研究院,重庆 401135,中国
    c南洋理工大学化工与生物技术学院, 新加坡
  • 收稿日期:2026-01-07 接受日期:2026-03-02 出版日期:2026-10-18 发布日期:2026-09-01
  • 通讯作者: *电子信箱: yiningwang@cust.edu.cn (王艺凝),
    wuyp@cust.edu.cn(吴云鹏),
    wangjw027@cust.edu.cn(王佳伟).
  • 基金资助:
    吉林省科技发展计划(DZJ202501ZYTS349);国家自然科学基金(22305024);国家自然科学基金(21972133)

Three-dimensional carbon foam and anion-vacancy synergistically modulate Ni-Fe bimetallic sulphides for efficient alkaline/seawater hydrogen evolution reactions

Ying Zhanga,1, Zengyuan Fana,1, Xiaohong Zhanga, Bo Zhaoa, Yining Wanga,*(), Yunpeng Wua,b,*(), Hiang Kwee Leec, Jiawei Wanga,b,*()   

  1. aJilin Provincial Science and Technology Innovation Centre of Optical Materials and Chemistry, Jilin Provincial International Joint Research Center of Photo-Functional Materials and Chemistry, School of Chemistry and Environmental Engineering, Changchun University of Science and Technology, Changchun 130022, Jilin, China
    bChongqing Research Institute, Changchun University of Science and Technology, Chongqing 401135, China
    cSchool of Chemistry, Chemical Engineering and Biotechnology, Nanyang Technological University, Singapore 639798, Singapore
  • Received:2026-01-07 Accepted:2026-03-02 Online:2026-10-18 Published:2026-09-01
  • Contact: *E-mail:yiningwang@cust.edu.cn(Y. Wang),wuyp@cust.edu.cn (Y. Wu),wangjw027@cust.edu.cn (J. Wang).
  • About author:First author contact:

    1 Contributed equally to this work.

  • Supported by:
    Science and Technology Development Planning of Jilin Province(DZJ202501ZYTS349);National Natural Science Foundation of China(22305024);National Natural Science Foundation of China(21972133)

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摘要：

贵金属(Pt/C)是经典析氢基准催化剂, 但铂储量稀缺、成本高昂, 限制其在电解水、海水电解规模化应用. 镍铁双金属硫化物因储量丰富、双金属电子协同效应显著, 成为非贵金属析氢反应(HER)催化剂的优选方向. 但传统镍铁硫化物存在比表面积小、导电性不佳等缺陷, 将其负载于高导电性基底(如碳材料)上并结合空位工程, 可大幅增加暴露的活性边缘位点, 显著提升电子转移效率. 因此, 采用负载型催化剂与空位工程策略协同调控催化剂的表面活性, 是构建稳定、高性能HER催化剂的有效途径.

本文以三聚氰胺泡沫为模板, 通过氧化石墨烯包覆与水热相结合的方法成功构筑出兼具高导电性与结构稳定性的三维多孔碳泡沫骨架(CF); 随后采用水热法原位合成Ni0.55Fe0.45S2催化剂, 并利用氟化铵刻蚀工艺引入硫空位, 最终制得硫空位与三维碳化泡沫协同调控的VS-Ni0.55Fe0.45S2@CF复合催化剂. 表征结果表明, 该催化剂保留了三维多孔结构, 且经硫空位调控后大幅提升了材料比表面积, 同时赋予其优异的超亲水性与疏气性, 显著提升了电解液的传质效率, 加速氢气气泡脱附, 避免活性位点堵塞. 深入的机理分析揭示了三维碳泡沫载体与硫空位的协同增效机制, 二者从电子传输、物理防护、表面电子调控及化学抗腐蚀等多维度实现了催化活性与稳定性的双重提升. 碳载体凭借优异的导电特性, 可构建高效的电子传输通道, 有效降低电极与催化剂之间的界面阻抗, 加速电催化过程中的电荷转移效率, 其相互连通的三维多孔网络结构还能形成物理屏障, 通过空间位阻效应阻碍电解液中的氯离子(Cl-)向催化活性位点迁移, 减少Cl-与活性中心的接触概率, 从物理层面缓解Cl-对催化剂的腐蚀作用, 保障催化结构的完整性. 硫空位可调控催化剂表面电子态, 优化氢中间体(H*)吸附能垒, 并诱导硫酸根离子生成, 通过静电排斥效应进一步抑制Cl-腐蚀, 从而协同提升催化活性与稳定性. 电化学性能测试结果表明, 在1.0 mol L-1氢氧化钾(KOH)电解液中, 该催化剂在10 mA cm-2电流密度下的过电位仅为51 mV, 且具备优异的长程稳定性(稳定运行250 h); 在模拟海水电解液(1.0 mol L-1 KOH + 0.5 mol L-1 NaCl)中, 其过电位为77 mV, 稳定性保持率超过70%, 有效克服了海水体系中Cl-腐蚀带来的性能衰减问题, 表现出良好的应用潜力.

综上, 本工作通过三维碳泡沫负载与硫空位工程的协同调控策略, 实现了碱性及海水体系下HER反应的高效、稳定进行. 该研究不仅突破了传统镍铁双金属硫化物的催化性能瓶颈, 还为非贵金属HER催化剂的结构设计提供了新的思路, 同时有效解决了海水电解制氢中的Cl-腐蚀难题.

关键词: 镍铁硫化物, 硫空位, 协同工程, 超亲水性, 三聚氰胺泡沫, 载体工程

Abstract:

To overcome the limitations of Pt/C catalysts in water and seawater electrolysis for hydrogen production, a anion vacancy-engineered bimetallic sulfide electrocatalyst was synthesized on a three-dimensional carbon foam support (VS-Ni0.55Fe0.45S2@CF) for highly efficient hydrogen evolution reaction (HER) under alkaline and seawater conditions. The catalyst utilizes melamine foam as a template, combining graphene oxide coating with hydrothermal carbonization to construct a three-dimensional porous carbon framework. Subsequently, the Ni0.55Fe0.45S2 catalyst is in-situ synthesized via hydrothermal methods, and sulfur vacancies are introduced through ammonium fluoride (NH4F) etching. Characterization revealed that the catalyst retained its three-dimensional porous structure, exhibiting outstanding superhydrophilicity and aerophobicity, significantly enhancing electrolyte mass transfer efficiency. Mechanistic analysis indicates that the high conductivity of carbon substrate effectively reduces electrode-catalyst interfacial resistance, while its porous structure physically blocks Cl- migration to active sites to suppress corrosion. Sulfur vacancies modulate the surface electronic states, optimize the H* adsorption energy barrier, and induce SO42- formation. This further inhibits Cl- corrosion through electrostatic repulsion, synergistically enhancing catalytic activity and stability. Consequently, in 1.0 mol L-1 KOH, this catalyst exhibits an overpotential of only 51 mV at a current density of 10 mA cm-2 and demonstrates long-term durability (operating stably for 250 h). In simulated seawater (1.0 mol L-1 KOH + 0.5 mol L-1 NaCl), the overpotential is 77 mV with a current retention rate exceeding 70% after long-term operation. This study provides experimental support for developing low-cost, highly efficient HER catalysts and provide a basis for large-scale green hydrogen production.

Key words: Nickel iron sulfide, Sulfur vacancies, Synergistic engineering, Superhydrophilicity, Melamine foam, Vector engineering