氢键网络动态优化与静电排斥协同抗氯用于碱性海水氧化

doi:10.1016/S1872-2067(26)65100-5

催化学报 ›› 2026, Vol. 87: 295-304.DOI: 10.1016/S1872-2067(26)65100-5

氢键网络动态优化与静电排斥协同抗氯用于碱性海水氧化

左玮^a^,¹, 刘明钰^a^,¹, 孙圣钧^a, 杨雨^b, 李子霄^a, 张习习^a, 杨朝鑫^a, 王和峰^a, 刘雪飞^b^,^*(), 刘倩^d^,^*(), 孙旭平^a^,^e^,^*(), 唐波^a^,^f

^a 山东师范大学化学化工与材料科学学院, 山东济南 250014, 中国
^b 贵州师范大学物理与电子科学学院, 贵州贵阳 550025, 中国
^c 麦地那伊斯兰大学理学院, 物理系, 麦地那, 沙特阿拉伯
^d 成都大学高等研究院, 四川成都 610106, 中国
^e 四川大学华西医院高原医学中心, 四川成都 610041, 中国
^f 崂山实验室, 山东青岛 266237, 中国

收稿日期:2026-01-09 接受日期:2026-02-06 出版日期:2026-08-18 发布日期:2026-06-24
通讯作者: ^*电子信箱: xpsun@uestc.edu.cn (孙旭平),
201307129@gznu.edu.cn (刘雪飞),
liuqian@cdu.edu.cn (刘倩).
作者简介:¹共同第一作者.

Synergistic chloride resistance via hydrogen‒bond network dynamic optimization and electrostatic repulsion for alkaline seawater oxidation

Wei Zuo^a^,¹, Mingyu Liu^a^,¹, Shengjun Sun^a, Yu Yang^b, Zixiao Li^a, Xixi Zhang^a, Chaoxin Yang^a, Hefeng Wang^a, Imran Shakir^c, Xuefei Liu^b^,^*(), Qian Liu^d^,^*(), Xuping Sun^a^,^e^,^*(), Bo Tang^a^,^f

^a College of Chemistry, Chemical Engineering and Materials Science, Shandong Normal University, Jinan 250014, Shandong, China
^b School of Physics and Electronic Science, Guizhou Normal University, Guiyang 550025, Guizhou, China
^c Department of Physics, Faculty of Science, Islamic University of Madinah, Madinah 42351, Saudi Arabia
^d Institute for Advanced Study, Chengdu University, Chengdu 610106, Sichuan, China
^e Center for High Altitude Medicine, West China Hospital, Sichuan University, Chengdu 610041, Sichuan, China
^f Laoshan Laboratory, Qingdao 266237, Shandong, China

Received:2026-01-09 Accepted:2026-02-06 Online:2026-08-18 Published:2026-06-24
About author:¹Contributed equally to this work.

摘要/Abstract

摘要：

氢气被视为可持续与脱碳能源体系中的关键能源载体, 电解水制氢因兼具环境效益与经济效益, 已成为最具应用前景的绿色制氢技术. 鉴于淡水资源在全球水资源中占比极低, 无法满足大规模电解制氢的原料需求, 利用海水作为电解原料成为极具潜力的替代方案. 海水电解中的阳极析氧反应(OER)涉及动力学缓慢的四电子转移过程, 严重制约整体电解效率; 同时, 海水中Cl^-的存在会引发副反应并剧烈腐蚀催化剂, 成为长期稳定电解的核心挑战. 因此, 合理设计兼具高活性与高稳定性的海水氧化阳极催化剂至关重要.

层状双氢氧化物(LDH)在碱性电解液中展现出优异的析氧反应活性. 本文采用简单的电聚合策略, 在CoFe LDH表面原位构建了聚对苯二酚保护层. 在聚合过程中, CoFe LDH原位生成的高价金属中心(CoFeOOH)与PHQ中的酚羟基通过氢键网络相连接, 从而在泡沫镍基底上形成复合电催化剂(PHQ@CoFe LDH/NF). 该界面工程具有双重功能: 脱质子后的酚羟基形成负电荷界面排斥Cl^‒; 同时, 氢键网络通过调控优化界面水的组成比例, 促进高效H⁺/OH^-转移. X-射线吸收光谱和X-射线光电子能谱结果表明, PHQ@CoFe LDH/NF催化剂中Co³⁺含量更高, 这说明引入聚对苯二酚层使得材料整体的电子结构得到调控. 正如预期, PHQ@CoFe LDH/NF展现出优异的综合性能, 仅需335 mV的过电位即可驱动1 A cm^-2的电流密度, 较初始的CoFe LDH/NF电极显著降低63 mV, 也优于商用基准RuO₂/NF电极. 拉曼光谱和傅里叶变换交流伏安法结果进一步表明, 氢键网络能够稳定高价态物种并提高OER活性. 同时, 该催化剂展现出卓越稳定性, 在1 A cm^-2的电流密度下稳定运行1000 h, 在1.5和2 A cm^-2条件下均可稳定运行500 h. 为了彰显其在实际电解应用中的优越潜力, 组装了碱性阴离子交换膜水电解装置, 使用PHQ@CoFe LDH/NF作为阳极, 阴极使用商用Pt/C/NF电极进行测试, 在2.55 V的低电压下实现了1 A cm^-2的电流密度, 显著优于基准Pt/C/NF||RuO₂/NF. 无论连续和还是间歇运行模式下, 该电解槽均实现500 h稳定运行. 理论计算与实验结果共同证实, 协同静电排斥效应与氢键网络优化作用有效打破了活性与稳定性的权衡关系, 从而在碱性海水电解中同时实现了高反应活性与卓越耐腐蚀性能.

综上, 这项工作不仅为构建稳健的海水电解催化剂提供了合理的设计策略, 更凸显了构建多功能保护层在排斥Cl^‒、调控界面传质与稳定活性中心方面的关键作用, 通过界面工程调控实现增强活性与抑制腐蚀的双重目标的巨大潜力, 为进一步开发适用于实际海水电解的高效、长寿命催化剂奠定了理论基础与技术储备, 也为推动海洋可再生能源制氢技术的实用化进程提供了有力支撑.

关键词: 钴铁层状双氢氧化物, 碱性海水氧化, 阳极腐蚀, 静电排斥, 氢键网络

Abstract:

Seawater electrolysis, while promising for sustainable hydrogen production, is fundamentally challenged by the relentless chloride ions (Cl^-)-induced corrosion, which impairs catalyst stability during long-term operation. We report a polyhydroquinone (PHQ)-modified electrocatalyst, where the redox-active PHQ layer is firmly coated to CoFe layered double hydroxide (CoFe LDH) surface through a strong hydrogen-bond network. Theoretical calculations and characterization techniques collectively elucidate that the unique interface creates an in situ protective coating, which effectively optimizes the composition of the interfacial water and prevents Cl^- attack. Such a catalyst shows outstanding performance in alkaline seawater, requiring an overpotential of only 335 mV to reach 1 A cm^-2 and exhibiting remarkable durability for 2000 h even at high current densities (j = 1, 1.5, and 2 A cm^-2). Furthermore, the constructed alkaline anion exchange membrane water electrolyzer achieves a j of 1 A cm^-2 at a low voltage of 2.55 V, significantly outperforming the benchmark Pt/C/NF||RuO₂/NF.

Key words: CoFe layered double hydroxide, Alkaline seawater oxidation, Anodic corrosion, Electrostatic repulsion, Hydrogen?bond network

左玮, 刘明钰, 孙圣钧, 杨雨, 李子霄, 张习习, 杨朝鑫, 王和峰, 刘雪飞, 刘倩, 孙旭平, 唐波. 氢键网络动态优化与静电排斥协同抗氯用于碱性海水氧化[J]. 催化学报, 2026, 87: 295-304.

Wei Zuo, Mingyu Liu, Shengjun Sun, Yu Yang, Zixiao Li, Xixi Zhang, Chaoxin Yang, Hefeng Wang, Imran Shakir, Xuefei Liu, Qian Liu, Xuping Sun, Bo Tang. Synergistic chloride resistance via hydrogen‒bond network dynamic optimization and electrostatic repulsion for alkaline seawater oxidation[J]. Chinese Journal of Catalysis, 2026, 87: 295-304.

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图/表 5

Fig. 1. (a) Schematic illustration of the synthetic process of PHQ@CoFe LDH/NF. (b) Element analysis of electrolyte after electropolymerization. (c) XRD patterns. (d) FT-IR spectra. (e) SEM images of PHQ@CoFe LDH/NF. TEM (f) and high-resolution TEM (g) images of PHQ@CoFe LDH. (h) TEM image and corresponding elemental distributions of PHQ@CoFe LDH.

Fig. 2. (a) Co K-edge XANES spectra. (b) Co FT-EXAFS spectra. (c) High-resolution XPS spectra for PHQ@CoFe LDH and CoFe LDH in Co 2p regions. (d) Fe K-edge XANES spectra. (e) Fe FT-EXAFS spectra. (f) High-resolution XPS spectra for PHQ@CoFe LDH and CoFe LDH in Fe 2p regions.

Fig. 3. LSV curves (a) and Δη/Δlog|j| values (b) of three electrocatalysts in 1 mol L-1 KOH + seawater. (c) TOF and mass activities of three electrocatalysts. FTacV curves (d) and corresponding regions area (e). (f) In-situ Raman spectra. (g) Bode plots. (h) Eapp and Log (Aapp) values. (i) The free energy change diagram of OER process.

Fig. 4. (a) Long-term electrolysis of PHQ@CoFe LDH/NF and CoFe LDH/NF. (b) Comparison of electrolysis lifespans in alkaline seawater. (c) UV-vis absorption spectra of the electrolytes after stability test. (d) Zeta potentials. (e) Energy calculations for the adsorption of Cl*. (f) Schematic diagram of AEMWE. (g) Polarization curves. (h) Continuous stability measurement. (i) Intermittent electrolysis of Pt/C/NF||PHQ@CoFe LDH/NF with 12-h start-shutdown cycles.

Fig. 5. In-situ Raman spectra of PHQ@CoFe LDH/NF (a) and CoFe LDH/NF (b) at different potentials. The proportions of the water configuration for PHQ@CoFe LDH/NF (c) and CoFe LDH/NF (d). (e) Trends in interfacial water. LSV curves of PHQ@CoFe LDH/NF (f) and CoFe LDH/NF (g) in simulated alkaline seawater with different NaCl concentrations. (h) Comparison of electrolysis lifespan.

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氢键网络动态优化与静电排斥协同抗氯用于碱性海水氧化

Synergistic chloride resistance via hydrogen‒bond network dynamic optimization and electrostatic repulsion for alkaline seawater oxidation

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