Yang Yongping, Wang Shulin, Zhang Guikai, Li Xingyu, Wu Qikai, Liu Hao, Deng Ziliang, Han Xinyi, Zhang Shuailong, Dong Wenbo, Song Jiangnan, Chen Yabin, Gao Xiao, Yang Yao, Dong Juncai, Cao Liang, Zhao Zipeng
Beijing Key Laboratory of Construction Tailorable Advanced Functional Materials and Green Applications/ Experimental Center of Advanced Materials/ School of Materials Science and Engineering, Beijing Institute of Technology, Beijing, 100081, China.
Department of Chemistry, Zhejiang University, Hangzhou, Zhejiang, 310058, China.
Angew Chem Int Ed Engl. 2025 Aug 22:e202512848. doi: 10.1002/anie.202512848.
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 (Vs), which are randomly distributed in the nanocatalyst. Notably, the impact of V 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) with the presence of urea, showing the Vs distributed away from Se dopants, which is significantly different from the Se-doped Ru oxide synthesized without urea (Se-RuO), showing Vs distributed relatively close to the Se dopants. The Ur-Se-RuO demonstrates superior oxygen evolution reaction performance over Se-RuO. Particularly, Ur-Se-RuO delivers a low working voltage (1.62 V@1 A cm) and excellent durability (>1000 h@200 mA cm) in PEMWE tests. Experimental and theoretical results reveal that Vs engage in long-range cooperation with spatially decoupled Se dopants in Ur-Se-RuO, 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（Ru）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。尽管元素掺杂是提高稳定性的常用方法，但它会无意中诱导氧空位（Vs），这些氧空位随机分布在纳米催化剂中。值得注意的是，V分布对钌基催化剂稳定性的影响仍未得到解决。在此，我们通过在空气中退火氯化钌（III）和硒（Se）的混合物（Ur-Se-RuO）并添加尿素合成了硒掺杂的氧化钌，结果表明Vs远离硒掺杂剂分布，这与不添加尿素合成的硒掺杂氧化钌（Se-RuO）显著不同，后者的Vs相对靠近硒掺杂剂分布。Ur-Se-RuO表现出优于Se-RuO的析氧反应性能。特别是，在PEMWE测试中，Ur-Se-RuO具有较低的工作电压（1.62 V@1 A cm）和出色的耐久性（>1000 h@200 mA cm）。实验和理论结果表明，在Ur-Se-RuO中，Vs与空间解耦的硒掺杂剂进行长程协同，通过分子内氧耦合机制协同增强反应动力学，同时抑制晶格氧机制并抑制Ru溶解，这展示了一种在有前景的钌基催化剂中打破活性-稳定性权衡的新策略。
