Yongping Yang, Shulin Wang, Guikai Zhang, Xingyu Li, Qikai Wu, Hao Liu, Ziliang Deng, Xinyi Han, Prof. Shuailong Zhang, Wenbo Dong, Jiangnan Song, Prof. Yabin Chen, Prof. Xiao Gao, Prof. Yao Yang, Prof. Juncai Dong, Prof. Liang Cao, Prof. Zipeng Zhao
{"title":"Tailoring the Oxygen Vacancy Distribution in Se-Doped RuOx to Enhance Its Stability in Acidic Water Electrolysis","authors":"Yongping Yang, Shulin Wang, Guikai Zhang, Xingyu Li, Qikai Wu, Hao Liu, Ziliang Deng, Xinyi Han, Prof. Shuailong Zhang, Wenbo Dong, Jiangnan Song, Prof. Yabin Chen, Prof. Xiao Gao, Prof. Yao Yang, Prof. Juncai Dong, Prof. Liang Cao, Prof. Zipeng Zhao","doi":"10.1002/ange.202512848","DOIUrl":null,"url":null,"abstract":"<p>Developing durable ruthenium (Ru)-based catalysts for proton exchange membrane water electrolyzer (PEMWE) remains challenging due to irreversible Ru dissolution and lattice oxygen instability. Although elemental doping is a general method to improve stability, it inadvertently induces oxygen vacancies (V<sub>O</sub>s), which are randomly distributed in the nanocatalyst. Notably, the impact of V<sub>O</sub> distribution on the stability of Ru-based catalysts remains unresolved. Herein, we synthesized the Se-doped Ru oxide via annealing the mixture of ruthenium (III) chloride and selenium (Se) in the air (Ur-Se-RuO<sub>x</sub>) with the presence of urea, showing the V<sub>O</sub>s distributed away from Se dopants, which is significantly different from the Se-doped Ru oxide synthesized without urea (Se-RuO<sub>x</sub>), showing V<sub>O</sub>s distributed relatively close to the Se dopants. The Ur-Se-RuO<sub>x</sub> demonstrates superior oxygen evolution reaction performance over Se-RuO<sub>x</sub>. Particularly, Ur-Se-RuO<sub>x</sub> delivers a low working voltage (1.62 V@1 A cm<sup>−2</sup>) and excellent durability (>1000 h@200 mA cm<sup>−2</sup>) in PEMWE tests. Experimental and theoretical results reveal that V<sub>O</sub>s engage in long-range cooperation with spatially decoupled Se dopants in Ur-Se-RuO<sub>x</sub>, synergistically enhancing reaction kinetics via an intramolecular oxygen coupling mechanism, while inhibiting the lattice oxygen mechanism and suppressing Ru dissolution, which demonstrates a new strategy to break the activity–stability trade-off in promising Ru-based catalysts.</p>","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"137 41","pages":""},"PeriodicalIF":0.0000,"publicationDate":"2025-08-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Angewandte Chemie","FirstCategoryId":"1085","ListUrlMain":"https://onlinelibrary.wiley.com/doi/10.1002/ange.202512848","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"","JCRName":"","Score":null,"Total":0}
引用次数: 0
Abstract
Developing durable ruthenium (Ru)-based catalysts for proton exchange membrane water electrolyzer (PEMWE) remains challenging due to irreversible Ru dissolution and lattice oxygen instability. Although elemental doping is a general method to improve stability, it inadvertently induces oxygen vacancies (VOs), which are randomly distributed in the nanocatalyst. Notably, the impact of VO distribution on the stability of Ru-based catalysts remains unresolved. Herein, we synthesized the Se-doped Ru oxide via annealing the mixture of ruthenium (III) chloride and selenium (Se) in the air (Ur-Se-RuOx) with the presence of urea, showing the VOs distributed away from Se dopants, which is significantly different from the Se-doped Ru oxide synthesized without urea (Se-RuOx), showing VOs distributed relatively close to the Se dopants. The Ur-Se-RuOx demonstrates superior oxygen evolution reaction performance over Se-RuOx. Particularly, Ur-Se-RuOx delivers a low working voltage (1.62 V@1 A cm−2) and excellent durability (>1000 h@200 mA cm−2) in PEMWE tests. Experimental and theoretical results reveal that VOs engage in long-range cooperation with spatially decoupled Se dopants in Ur-Se-RuOx, synergistically enhancing reaction kinetics via an intramolecular oxygen coupling mechanism, while inhibiting the lattice oxygen mechanism and suppressing Ru dissolution, which demonstrates a new strategy to break the activity–stability trade-off in promising Ru-based catalysts.
由于钌的不可逆溶解和晶格氧的不稳定性,开发用于质子交换膜水电解槽(PEMWE)的耐用钌基催化剂仍然具有挑战性。虽然元素掺杂是提高稳定性的一种常用方法,但它会无意中引起氧空位(VOs),这些空位在纳米催化剂中是随机分布的。值得注意的是,VO分布对ru基催化剂稳定性的影响仍未得到解决。本文将氯化钌(III)和硒(Se)的混合物(Ur-Se-RuOx)在空气中退火,在尿素存在的情况下合成了掺硒氧化钌(Ur-Se-RuOx),显示出VOs远离Se掺杂剂的分布,这与不含尿素合成的掺硒氧化钌(Se- ruox)明显不同,显示出VOs相对靠近Se掺杂剂的分布。Ur-Se-RuOx表现出比Se-RuOx更好的析氧反应性能。特别是,Ur-Se-RuOx在PEMWE测试中提供低工作电压(1.62 V@1 a cm−2)和出色的耐久性(>1000 h@200 mA cm−2)。实验和理论结果表明,VOs与Ur-Se-RuOx中空间解耦的Se掺杂物长期合作,通过分子内氧偶联机制协同提高反应动力学,同时抑制晶格氧机制和抑制Ru的溶解,这表明了一种新的策略来打破有前途的Ru基催化剂的活性-稳定性平衡。