Chloride-Induced Active Site Transfer and Mechanism Switching for Efficient and Stable Oxygen Evolution in Acidic Seawater Electrolysis

IF 7.6 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

ACS Sustainable Chemistry & Engineering Pub Date : 2026-10-15 DOI:10.1021/acssuschemeng.6c06834

Yanru Geng,Liqiang Hou,Chaoyue Sun,Zhaoyue Zhang,Liang Yang,Haeseong Jang,Min Gyu Kim,Xien Liu

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引用次数: 0

Abstract

Abstract Direct seawater electrolysis for green hydrogen is hindered by Ca2+/Mg2+ precipitation in neutral/alkaline systems. Acidic electrolysis avoids this, yet suffers from sluggish oxygen evolution reaction (OER) kinetics, competitive chlorine evolution reaction (CER) from chloride ions, and severe catalyst corrosion. Herein, we construct a Ru/WO3 catalyst with abundant Ru–O–W interfacial bonds for simulated acidic seawater (0.5 M H2SO4 + 0.5 M NaCl). The catalyst requires only 153 mV overpotential to deliver 10 mA cm–2 and operates stably for over 600 h. Notably, excellent performance is also maintained in acidified natural seawater, achieving stable operation at 500 mA cm–2 for 200 h. Remarkably, the introduction of Cl– does not trigger severe chlorine evolution side reactions; instead, it enhances OER selectivity to 93.6% and reduces Ru and W dissolution by approximately 79% and 84%, respectively, relative to the pure acid condition. Mechanistic studies reveal that Cl– preferentially adsorbs on Ru sites to form a Ru–Cl protective layer, blocking OH– attack and high-valent Ru dissolution that occur in the conventional adsorbate evolution mechanism (AEM). Consequently, the active site transfers to adjacent W sites and Ru–O–W bridging oxygen, and the reaction proceeds via the lattice oxygen oxidation mechanism (LOM) to accomplish O–O coupling.

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酸性海水电解高效稳定析氧的氯诱导活性位点转移及机制切换

在中性/碱性体系中，Ca2+/Mg2+沉淀阻碍了绿色氢的直接海水电解。酸性电解避免了这种情况，但会受到缓慢的析氧反应（OER）动力学、氯离子的竞争性析氯反应（CER）和严重的催化剂腐蚀的影响。本文构建了一种具有丰富Ru - o - w界面键的Ru/WO3催化剂，用于模拟酸性海水（0.5 M H2SO4 + 0.5 M NaCl）。该催化剂只需要153 mV过电位就能提供10 mA cm-2，稳定运行超过600小时。值得注意的是，在酸化的天然海水中也保持了优异的性能，在500 mA cm-2下稳定运行200小时。值得注意的是，Cl -的引入不会引发严重的氯析出副反应；相反，与纯酸条件相比，OER选择性提高到93.6%，Ru和W的溶解分别减少了约79%和84%。机理研究表明，Cl -优先吸附在Ru位点形成Ru - Cl保护层，阻断了常规吸附演化机制（AEM）中OH -的攻击和高价Ru的溶解。因此，活性位点转移到相邻的W位点和Ru-O-W桥接氧上，并通过晶格氧氧化机制（LOM）进行反应，实现O-O偶联。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

ACS Sustainable Chemistry & Engineering CHEMISTRY, MULTIDISCIPLINARY-ENGINEERING, CHEMICAL

CiteScore

13.80

自引率

4.80%

发文量

1470

审稿时长

1.7 months

期刊介绍： ACS Sustainable Chemistry & Engineering is a prestigious weekly peer-reviewed scientific journal published by the American Chemical Society. Dedicated to advancing the principles of green chemistry and green engineering, it covers a wide array of research topics including green chemistry, green engineering, biomass, alternative energy, and life cycle assessment. The journal welcomes submissions in various formats, including Letters, Articles, Features, and Perspectives (Reviews), that address the challenges of sustainability in the chemical enterprise and contribute to the advancement of sustainable practices. Join us in shaping the future of sustainable chemistry and engineering.