稀土/钴共掺杂相限域构筑稳定RuO2(110)主导构型及其高效酸性析氧催化

doi:10.1016/S1872-2067(26)65270-9

催化学报 ›› 2027, Vol. 92: 182-191.DOI: 10.1016/S1872-2067(26)65270-9

稀土/钴共掺杂相限域构筑稳定RuO₂(110)主导构型及其高效酸性析氧催化

皮拉查·桑瓦尔^a^,^d, 张静静^b^,^*(), 拉希德·迈赫穆德^a, 孙林坤^b, 胡绪^c, 戴文^a^,^*(), 李杲^b^,^*()

^a 中国科学院大连化学物理研究所, 辽宁大连 116023
^b 内蒙古师范大学化学与环境科学学院, 内蒙古呼和浩特 010022
^c 南开大学材料科学与工程学院, 新能源材料化学研究所, 可再生能源转换与储能中心, 教育部先进能源材料化学重点实验室, 天津 300350
^d 中国科学院大学, 北京 100049

收稿日期:2026-04-24 接受日期:2026-07-03 出版日期:2027-01-02 发布日期:2026-10-30
通讯作者: *电子信箱: daiwen@dicp.ac.cn (戴文),
li_gao82@yeah.net (李杲),
jjzhang21111@163.com (张静静).
基金资助:
国家自然科学基金(223B2305);内蒙古自治区科技领军人才团队培育专项项目;内蒙古自治区“两个屏障”、“两个基地”、“一个桥头堡”关键领域科技创新研究专项(NMGLLY2025-01)

Dopant-enabled RuO₂(110)-dominant architecture for boosting sustainable acidic oxygen evolution

Piracha Sanwal^a^,^d, Jingjing Zhang^b^,^*(), Rashid Mehmood^a, Linkun Sun^b, Xu Hu^c, Wen Dai^a^,^*(), Gao Li^b^,^*()

^a Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China
^b School of Chemistry and Chemical Engineering, Inner Mongolia Normal University, Hohhot 010022, Inner Mongolia, China
^c School of Materials Science and Engineering, Institute of New Energy Material Chemistry, Renewable Energy Conversion and Storage Centre (ReCast), Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), Nankai University, Tianjin 300350, China
^d University of Chinese Academy of Sciences, Beijing 100049, China

Received:2026-04-24 Accepted:2026-07-03 Online:2027-01-02 Published:2026-10-30
Contact: *E-mail: daiwen@dicp.ac.cn (W. Dai),
li_gao82@yeah.net (G. Li),
jjzhang21111@163.com (J. Zhang).
About author:First author contact:CRediT authorship contribution statement
Piracha Sanwal: Writing-original draft, Visualization, Supervision, Formal analysis. Jingjing Zhang: Visualization, Validation, Software, Writing-original draft. Rashid Mehmood: Visualization, Software. Linkun Sun: Visualization, Validation. Xu Hu: Software, Funding acquisition, Writing-review &editing. Wen Dai: Visualization, Validation, Funding acquisition, Writing-review &editing. Gao Li: Writing-review &editing, Supervision, Project administration, Conceptualization.
Supported by:
National Natural Science Foundation of China(223B2305);Project for the Cultivation of Science and Technology Leading Talent Teams in Inner Mongolia Autonomous Region;the Implementation Plan for Scientific and Technological Innovation in Key Areas of the Inner Mongolia Autonomous Region(NMGLLY2025-01)

摘要/Abstract

摘要：

酸性介质中的析氧反应(OER)长期面临活性与稳定性难以兼得的挑战. 作为酸性OER的标杆催化剂, RuO₂虽具有优异的初始活性, 但其实际工况下Ru物种的持续溶解导致催化性能急剧衰减, 严重制约了其规模化应用. 理论与计算研究已揭示, RuO₂(110)晶面展现出显著的OER本征活性优势, 但其在氧化电位下的结构退化问题尚未得到有效解决. 近期研究表明, 精准调控(110)表面的重构行为, 是调控Ru-O共价键强度、优化OER反应路径能垒、并提升结构韧性的关键所在. 为此, 本文创新性地提出稀土-钴共掺杂相限域策略, 通过选择性稳定RuO₂(110)主导晶面, 构建兼具高催化活性与长期运行稳定性的酸性OER催化体系.

本研究采用碳纳米管(CNTs)作为模板, 经由水热-煅烧工艺制备了Ce/Co共掺杂RuO₂催化剂(CeCo-RuO₂). 多种互补表征技术(X射线衍射、高角环形暗场扫描透射电镜、拉曼光谱、X射线光电子能谱及X射线吸收谱)一致证实, Co与Ce原子均匀地嵌入RuO₂体相晶格之中. 电化学测试表明, 该催化剂在10 mA cm^-2下过电位仅为~198 mV, 显著优于商业RuO₂; 在100和200 mA cm^-2的高电流密度下, 分别可稳定运行500和120 h, 失活速率低至0.04 mV h^-1, 展现出迄今为止报道的钌基催化剂中极具竞争力的OER催化性能(活性及稳定性). 系统电化学分析表明, CeCo-RuO₂实现了电化学活性面积、反应动力学、过电位与耐久性之间的协同优化. 机理研究表明, Ce/Co共掺杂诱导的界面氧化还原缓冲效应, 有效抑制了Ru的过度氧化与溶解, 将Ru稳定于有利于OER催化过程的电子态. 值得关注的是, 原子力显微镜原位追踪揭示了OER工况下催化剂表面由光滑向高纹理化(显著粗糙度与纳米级凸起)的剧烈重构, 该重构与RuO₂(110)类活性基元的形成密切相关. 结合原位红外、差分电化学质谱、探针实验与理论计算, 进一步明确其酸性OER路径以吸附质介导机理主导. 本研究提出的掺杂诱导相限域与表面重构协同策略, 为开发高稳定酸性OER催化剂提供了重要理论依据与实验支撑.

综上, 本工作表明掺杂驱动的重构是获得稳定的RuO₂(110)类活性相和稳定相的有效方法, 并为设计高效的酸性OER催化剂提供了新思路.

关键词: RuO₂(110)晶面, 酸性析氧, Ce/Co掺杂, 吸附质介导机理, 密度泛函理论

Abstract:

Although Ru-based catalysts have been widely exploited in oxygen evolution reaction (OER), they still face significant challenges in simultaneously achieving high activity and long-term stability. Here, we propose a catalyst design strategy that engineers phases beyond conventional atomic ordering by constructing a RuO₂(110)-dominated architecture (CeCo-RuO₂). The resulting catalyst exhibits an overpotential of 198 mV@10 mA cm^-2 and exceptional durability, operating stably for over 500 h at a current density of 100 mA cm^-2 with a minimal current decay rate of 0.04 mV h^-1. The engineered RuO₂phase architecture and atomic arrangement induce electronic structure reconfiguration, thereby optimizing active-site density and structural robustness. In-situ characterization combined with density functional theory calculations reveal that CeCo-RuO₂ preferentially follows adsorbate evolution mechanism with reduced energy barriers, thereby suppressing lattice oxygen participation and mitigating structural instability. In all, we demonstrate dopant-enabled phase confinement as an effective design strategy for developing active and durable OER catalysts.

Key words: RuO₂(110), Acidic oxygen evolution, Ce/Co-dopant, Adsorbate evolution mechanism, Density functional theory

皮拉查·桑瓦尔, 张静静, 拉希德·迈赫穆德, 孙林坤, 胡绪, 戴文, 李杲. 稀土/钴共掺杂相限域构筑稳定RuO₂(110)主导构型及其高效酸性析氧催化[J]. 催化学报, 2027, 92: 182-191.

Piracha Sanwal, Jingjing Zhang, Rashid Mehmood, Linkun Sun, Xu Hu, Wen Dai, Gao Li. Dopant-enabled RuO₂(110)-dominant architecture for boosting sustainable acidic oxygen evolution[J]. Chinese Journal of Catalysis, 2027, 92: 182-191.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(26)65270-9

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图/表 8

Fig. 1. Schematic synthesis (a), high-resolution STEM image (b) with elemental mappings (c), and elemental line-scan profile (d) of CeCo-RuO2.

Fig. 2. The physical characterization of pristine CeCo-RuO2 and RuO2: powder XRD patterns (a), XPS spectra (Ce 3d (b) and Co 2p (c)), and Raman spectra (d).

Fig. 3. LSV curves (a) and overpotential statistics (b) at 10 and 100 mA cm-2 of RuO2 and CeCo-RuO2. Tafel (c) and Nyquist plots (d). (e) Durability of CeCo-RuO2 at 100 and 200 mA cm-2. (f) Cdl plots. (g) Benchmark comparison of CeCo-RuO2 with recently reported acidic OER catalysts.

Fig. 4. HR-STEM image (a) with EDS mapping (b) and XRD patterns (c) of utilized CeCo-RuO2 after OER test.

Fig. 5. AFM images of pristine utilized CeCo-RuO2 (a) and after OER (b‒d) at different regions

Fig. 6. The spectroscopic comparison of pristine and utilized CeCo-RuO2: Ru 3p (a) and O 1s (b) XPS, Raman (c), and EPR (d) spectra.

Fig. 7. In-situ FTIR spectra of CeCo-RuO2 (a) and RuO2 (d) recorded from 0.9 to 1.8 V vs. RHE in the 800-1800 cm-1 region. (b) Comparison of FTIR spectra at selected potentials. (c) In-situ FTIR spectra of CeCo-RuO2 in the O-H stretching region (3000-4000 cm-1).

Fig. 8. (a,b) Structural models of Ce-RuO2(110) and amorphous RuO2. (c) Representative slab model of CeCo-RuO2. (d) Schematic illustration of the AEM pathway. Calculated OER free-energy diagrams (e) and chloride adsorption energies (f) for CeCo-RuO2(110) and amorphous RuO2.

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稀土/钴共掺杂相限域构筑稳定RuO₂(110)主导构型及其高效酸性析氧催化

Dopant-enabled RuO₂(110)-dominant architecture for boosting sustainable acidic oxygen evolution

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