文献类型：期刊文献

英文题名：An asymmetric RE-O-Ru unit with bridged oxygen vacancies accelerates deprotonation during acidic water oxidation

作者：Wang, Caikang[1,2] Wu, Xiangrui[1] Sun, Hao[2] Xu, Zhe[1] Xu, Chang[1] Wang, Xuan[1] Li, Meng[1] Wang, Yu[1] Tang, Yawen[1] Jiang, Jianchun[2] Sun, Kang[2] Fu, Gengtao[1]

第一作者：Wang, Caikang

通信作者：Fu, GT[1];Sun, H[2];Sun, K[2]

机构：[1]Nanjing Normal Univ, Jiangsu Collaborat Innovat Ctr Biomed Funct Mat, Sch Chem & Mat Sci, Jiangsu Key Lab New Power Batteries, Nanjing 210023, Peoples R China;[2]Chinese Acad Forestry, Inst Chem Ind Forest Prod, Key Lab Biomass Energy & Mat, Key & Open Lab Forest Chem Engn,SFA,Natl Engn Lab, Nanjing 210042, Jiangsu, Peoples R China

年份：2025

外文期刊名：ENERGY & ENVIRONMENTAL SCIENCE

收录：;EI(收录号：20251418177186);Scopus(收录号：2-s2.0-105001732596);WOS:【SCI-EXPANDED(收录号:WOS:001454676700001)】；

基金：This work was financially supported by the National Key R&D Program (2023YFB4203705). The authors are grateful for the support from the National and Local Joint Engineering Research Center of Biomedical Functional Materials and a project sponsored by the Priority Academic Program Development of Jiangsu Higher Education Institutions.

语种：英文

外文关键词：Bioremediation - Ion exchange membranes - Lutetium alloys - Neodymium alloys - Oxygen permeable membranes - Photodegradation - Photodissociation - Ruthenium - Ruthenium alloys - Ruthenium compounds - Samarium alloys - Samarium compounds

摘要：Proton exchange membrane water electrolysis (PEMWE) is a promising technology for sustainable hydrogen production; however, the slow deprotonation of oxo-intermediates on RuO2 during the acidic oxygen evolution reaction (OER) limits its long-term stability. Herein, we propose an innovative and effective rare-earth (RE)-mediated strategy to accelerate the deprotonation of OER intermediates on the RuO2 matrix by constructing an asymmetric RE-O-Ru structural unit. Taking Sm as a RE model, the incorporation of Sm into RuO2 induces the formation of an asymmetric Sm-O-Ru unit with a unique f-p-d electron ladder and an adjacent bridged oxygen vacancy (Ov), which compensates for electron loss in Ru species and creates vacancy-localized electronic perturbation at the bridged Ov due to the delocalization of 4f electrons. The optimized Sm-RuO2-x-Ov catalyst requires an overpotential of only 217 mV at 10 mA cm-2 and operates steadily for over 300 h with a negligible degradation rate of similar to 27 mu V h-1 in an acidic medium, outperforming Sm-free RuO2 and most other reported Ru-based catalysts. In situ characterization and theoretical analysis demonstrate that the constructed asymmetric Sm-O-Ru unit prevents the over-oxidation of Ru species at high voltages and accelerates the *OH deprotonation at the surface oxygen vacancy during the OER process, leading to high OER activity and stability. The potential role of asymmetric RE-O-Ru units with bridged Ov is also observed in other RE-doped RuO2 systems (e.g., Nd and Lu), where all catalysts exhibit enhanced deprotonation of oxygenated intermediates. We believe that the RE-mediated strategy presented in this work provides a new pathway for designing highly active and stable noble-metal-based catalysts for acidic water oxidation.