通过铜诱导的表面重构动态调节钌催化剂中酸性析氧反应途径

doi:10.1016/S1872-2067(26)64970-4

催化学报 ›› 2026, Vol. 83: 363-375.DOI: 10.1016/S1872-2067(26)64970-4

通过铜诱导的表面重构动态调节钌催化剂中酸性析氧反应途径

Hyunseok Yoon^a^,¹, Hee Jo Song^b^,¹, Yumin Park^a, Andi Haryanto^c, Dohun Kim^d, Kyuri Cho^e, Chanyeon Kim^d, Wooyul Kim^e, Chan Woo Lee^c, Dong-Wan Kim^a^,^*()

^a韩国大学土木、环境与建筑工程学院, 首尔, 韩国
^b世宗大学纳米技术与先进材料工程系, 首尔, 韩国
^c国民大学化学系, 首尔, 韩国
^d大邱庆北科学技术院, 能源科学与工程系, 大邱, 韩国
^e韩国能源技术研究所能源工程系, 全罗南道那州, 韩国

收稿日期:2025-09-11 接受日期:2025-11-04 出版日期:2026-04-18 发布日期:2026-03-04
通讯作者: * 电子信箱: dwkim1@korea.ac.kr (D.-W. Kim).
作者简介:¹共同第一作者.

Dynamic tuning of acidic oxygen evolution reaction pathways in Ru catalysts via Cu-induced surface restructuring

Hyunseok Yoon^a^,¹, Hee Jo Song^b^,¹, Yumin Park^a, Andi Haryanto^c, Dohun Kim^d, Kyuri Cho^e, Chanyeon Kim^d, Wooyul Kim^e, Chan Woo Lee^c, Dong-Wan Kim^a^,^*()

^aSchool of Civil, Environmental and Architectural Engineering, Korea University, Seoul 02841, South Korea
^bDepartment of Nanotechnology and Advanced Materials Engineering, Sejong University, Seoul 05006, South Korea
^cDepartment of Chemistry, Kookmin University, Seoul 02707, South Korea
^dDepartment of Energy Science & Engineering, DGIST, Daegu 42988, South Korea
^eDepartment of Energy Engineering, Korea Institute of Energy Technology (KENTECH), Naju, Jeollanam-do 58330, South Korea

Received:2025-09-11 Accepted:2025-11-04 Online:2026-04-18 Published:2026-03-04
Contact: * E-mail: dwkim1@korea.ac.kr (D.-W. Kim).
About author:¹Contributed equally to this work.

摘要/Abstract

摘要：

在酸性介质中实现析氧反应(OER)的高活性和长期稳定性仍然是质子交换膜水电解槽(PEMWE)面临的关键挑战. 本文提出了一种掺Cu的Ru催化剂(CuRu-250, 退火温度在250 °C), 该催化剂在操作过程中通过动态表面调制, 表现出优异的性能. Cu不仅是一种静态掺杂剂, 而是通过经历部分溶解和诱导表面重组来积极影响催化剂表面. 这种动态行为使路径从吸附物演化机制调整为氧化物路径机制, 从而促进了中间转换并抑制了Ru的过氧化. 因此, 与未掺杂的Ru和商业RuO₂相比, CuRu-250表现出显著提高的耐久性和优异的活性. 单电池PEMWE测试验证了其在实际条件下的催化性能. 这些发现强调了活性掺杂剂行为在调节酸性OER途径和提高电化学稳定性方面的作用, 从而为先进的催化剂设计提供了一种有效的策略.

关键词: 钌, 动态表面重构, 析氧反应, 质子交换膜水电解器, 氧化路径机制

Abstract:

Achieving both high activity and long-term stability for the oxygen evolution reaction (OER) in acidic media remains a critical challenge for proton exchange membrane water electrolyzers (PEMWEs). In this study, we proposed a Cu-incorporated ruthenium (Ru) catalyst (CuRu-250) that exhibited superior performance via dynamic surface modulation during operation. Rather than serving solely as a static dopant, Cu actively influenced the catalyst surface by undergoing partial dissolution and inducing surface restructuring. This dynamic behavior enabled pathway tuning from the adsorbate evolution mechanism to the oxide path mechanism, enhancing the intermediate turnover and suppressing the overoxidation of Ru. Consequently, CuRu-250 demonstrated markedly improved durability and competitive activity compared to undoped Ru and commercial RuO₂. Single-cell PEMWE tests validated its catalytic performance under realistic conditions. These findings highlight the role of active dopant behavior in tuning acidic OER pathways and improving electrochemical resilience, thus offering a practical strategy for advanced catalyst design.

Key words: Ruthenium, Dynamic surface restructuring, Oxygen evolution reaction, Proton exchange membrane water electrolyzer, Oxide path mechanism

Hyunseok Yoon, Hee Jo Song, Yumin Park, Andi Haryanto, Dohun Kim, Kyuri Cho, Chanyeon Kim, Wooyul Kim, Chan Woo Lee, Dong-Wan Kim. 通过铜诱导的表面重构动态调节钌催化剂中酸性析氧反应途径[J]. 催化学报, 2026, 83: 363-375.

Hyunseok Yoon, Hee Jo Song, Yumin Park, Andi Haryanto, Dohun Kim, Kyuri Cho, Chanyeon Kim, Wooyul Kim, Chan Woo Lee, Dong-Wan Kim. Dynamic tuning of acidic oxygen evolution reaction pathways in Ru catalysts via Cu-induced surface restructuring[J]. Chinese Journal of Catalysis, 2026, 83: 363-375.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(26)64970-4

https://www.cjcatal.com/CN/Y2026/V83/I4/363

图/表 6

Scheme 1. Schematic illustration of the dynamic surface modulation of Ru catalysts induced by Cu incorporation.

Fig. 1. (a,b) SEM micrographs of a CuRu-250 synthesized on Ti mesh substrate. (c) The cross-sectional SEM image and corresponding EDS analysis of CuRu-250. HR-TEM image (d) and corresponding electron diffraction pattern (e) of CuRu-250. (f) TEM-EDS elemental mapping of CuRu-250. (g) XRD patterns of Ru-250 and CuRu-250. (h) Ru 3d and (i) Cu 2p XPS spectra of Ru-250 and CuRu-250, respectively.

Fig. 2. (a) The OER polarization curves of Ru-250, CuRu-250 and Comm-RuO2 in 0.5 mol L?1 H2SO4 electrolyte. (b) Chronopotentiometric stability tests of Ru-250 and CuRu-250. (c) Dissolved metal elements concentration in electrolyte for Ru-250 and CuRu-250 determined via ICP-MS. (d) Calculated S-number for Ru-250 and CuRu-250 in acidic OER. (e) The comparison of the required overpotential at 10 mA cm?2 and stability in acidic OER for previous reported electrocatalysts. (Table S2).

Fig. 3. Operando DEMS signals of O2 products for Ru-250 (a) and CuRu-250 (b). (c) Atomistic structure for key reaction steps in the AEM and OPM reaction pathways. The free energy diagrams for acidic OER based on each AEM and OPM reaction pathways of Ru-250 (d) and CuRu-250 (e) at 1.23 V vs. RHE.

Fig. 4. Operando ATR-SEIRAS measurements in the range of 900?1300 cm?1 at various applied potentials for Ru-250 (a) and CuRu-250 (b). Contour plots of in-situ electrochemical Raman spectroscopy of Ru-250 (c) and CuRu-250 (d) in 0.5 mol L?1 H2SO4.

Fig. 5. (a) Schematic illustration of the stack structure and operation principle of PEMWE. (b) The cross-sectional SEM image and corresponding EDS mapping of the MEA prepared using CuRu-250 as anode. (c) I-V curves of PEMWE with Ru-250, CuRu-250 and Comm-RuO2 as anode without iR compensation. (d) Chronoamperometry curves of the PEMWE at 1.35 V using Ru-250 and CuRu-250 as anode.

参考文献

[1]	S. Imran, M. Hussain, Int. J. Hydrogen Energy, 2024, 77, 975-996.
[2]	H. Zhao, Z.-Y. Yuan, Adv. Energy Mater., 2023, 13, 2300254.
[3]	N. S. Hassan, A. A. Jalil, S. Rajendran, N. F. Khusnun, M. B. Bahari, A. Johari, M. J. Kamaruddin, M. Ismail, Int. J. Hydrogen Energy, 2024, 52, 420-441.
[4]	R.-T. Liu, Z.-L. Xu, F.-M. Li, F.-Y. Chen, J.-Y. Yu, Y. Yan, Y. Chen, B.-Y. Xia, Chem. Soc. Rev., 2023, 52, 5652-5683.
[5]	C. R. Wang, J. M. Stansberry, R. Mukundan, H. J. Chang, D. Kulkarni, A. M. Park, A. B. Plymill, N. M. Firas, C. P. Liu, J. T. Lang, J. K. Lee, N. E. Tolouei, Y. Morimoto, C. H. Wang, G. Zhu, J. Brouwer, P. Atanassov, C. B. Capuano, C. Mittelsteadt, X. Peng, I. V. Zenyuk, Chem. Rev., 2025, 125, 1257-1302.
[6]	N.-T. Suen, S.-F. Hung, Q. Quan, N. Zhang, Y.-J. Xu, H.-M. Chen, Chem. Soc. Rev., 2017, 46, 337-365.
[7]	L. Li, P. Wang, Q. Shao, X. Huang, Adv. Mater., 2021, 33, 2004243.
[8]	F.-Y. Chen, Z.-Y. Wu, Z. Adler, H. Wang, Joule, 2021, 5, 1704-1731.
[9]	Q. Wang, Y. Cheng, H.-B. Tao, Y. Liu, X. Ma, D.-S. Li, H.-B. Yang, B. Liu, Angew. Chem. Int. Ed., 2023, 62, e202216645.
[10]	H. Wang, X. Li, G. Zhang, Z. Gu, H. Chen, G. Wei, S. Shen, J. Cheng, J. Zhang, Small, 2025, 21, 2410407.
[11]	W. Li, Y. Bu, X. Ge, F. Li, G.-F. Han, J.-B. Baek, ChemSusChem, 2024, 17, e202400295.
[12]	J. Li, J. Zeng, F. Zhao, X. Sun, S. Wang, X.-F. Lu, Energy Fuels, 2024, 38, 11521-11540.
[13]	L. Hou, X. Gu, X. Cui, J. Tang, Z. Li, X. Liu, J. Cho, EES Catal., 2023, 1, 619-644.
[14]	S. Li, S. Zhao, F. Hu, L. Li, J. Ren, L. Jiao, S. Ramakrishna, S. Peng, Prog. Mater. Sci., 2024, 145, 101294.
[15]	W. Gou, S. Zhang, Y. Wang, X. Tan, L. Liao, Z. Qi, M. Xie, Y. Ma, Y. Su, Y. Qu, Energy Environ. Sci., 2024, 17, 6755-6765.
[16]	G. Zhao, W. Guo, M. Shan, Y. Fang, G. Wang, M. Gao, Y. Liu, H. Pan, W. Sun, Adv. Mater., 2024, 36, 2404213.
[17]	H. Liu, Z. Zhang, J. Fang, M. Li, M. G. Sendeku, X. Wang, H. Wu, Y. Li, J. Ge, Z. Zhuang, D. Zhou, Y. Kuang, X. Sun, Joule, 2023, 7, 558-573.
[18]	C. Lin, J.-L. Li, X. Li, S. Yang, W. Luo, Y. Zhang, S.-H. Kim, D.-H. Kim, S. S. Shinde, Y.-F. Li, Z.-P. Liu, Z. Jiang, J.-H. Lee, Nat. Catal., 2021, 4, 1012-1023.
[19]	D. H. Kweon, M. S. Okyay, S.-J. Kim, J.-P. Jeon, H.-J. Noh, N. Park, J. Mahmood, J.-B. Baek, Nat. Commun., 2020, 11, 1278.
[20]	J. Ying, J.-B. Chen, Y.-X. Xiao, S. I. Cordoba de Torresi, K. I. Ozoemena, X.-Y. Yang, J. Mater. Chem. A, 2023, 11, 1634-1650.
[21]	Z.-L. Zhao, Q. Wang, X. Huang, Q. Feng, S. Gu, Z. Zhang, H. Xu, L. Zeng, M. Gu, H. Li, Energy Environ. Sci., 2020, 13, 5143-5151.
[22]	Y. Qin, T. Yu, S. Deng, X.-Y. Zhou, D. Lin, Q. Zhang, Z. Jin, D. Zhang, Y.-B. He, H.-J. Qiu, L. He, F. Kang, K. Li, T.-Y. Zhang, Nat. Commun., 2022, 13, 3784.
[23]	J. Tang, D. Guan, H. Xu, L. Zhao, U. Arshad, Z. Fang, T. Zhu, M. Kim, C.-W. Pao, Z. Hu, J. Ge, Z. Shao, Nat. Commun., 2025, 16, 801.
[24]	Y. Qin, R. Zhao, J. Sun, M. Xu, Q. Wang, Appl. Surf. Sci., 2023, 622, 156945.
[25]	T. Wang, Z. Li, H. Jang, M. G. Kim, Q. Qin, X. Liu, ACS Sustainable Chem. Eng., 2023, 11, 5155-5163.
[26]	Y. Liu, Y. Huang, D. Wu, H. Jang, J. Wu, H. Li, W. Li, F. Zhu, M. G. Kim, D. Zhou, X. Xi, Z. Lei, Y. Zhang, Y. Deng, W. Yan, M. D. Gu, J. Jiang, S. Jiao, R. Cao, J. Am. Chem. Soc., 2024, 146, 26897-26908.
[27]	J. Chen, Y. Ma, T. Huang, T. Jiang, S. Park, J. Xu, X. Wang, Q. Peng, S. Liu, G. Wang, W. Chen, Adv. Mater., 2024, 36, 2312369.
[28]	L. An, F. Yang, C. Fu, X. Cai, S. Shen, G. Xia, J. Li, Y. Du, L. Luo, J. Zhang, Adv. Funct. Mater., 2022, 32, 2200131.
[29]	K.-R. Yeo, H. Kim, K.-S. Lee, S. Kim, J. Lee, H. Park, S.-K. Kim, Appl. Catal. B, 2024, 346, 123738.
[30]	C. Rong, K. Dastafkan, Y. Wang, C. Zhao, Adv. Mater., 2023, 35, 2211884.
[31]	H. Zhang, L. Chen, F. Dong, Z. Lu, E. Lv, X. Dong, H. Li, Z. Yuan, X. Peng, S. Yang, J. Qiu, Z. Guo, Z. Wen, Energy Environ. Sci., 2024, 17, 6435-6481.
[32]	Z. Liu, X. Wang, G. Xie, J. Ge, Chem. Eng. J., 2024, 499, 155901.
[33]	C. Spöri, J. T. H. Kwan, A. Bonakdarpour, D. P. Wilkinson, P. Strasser, Angew. Chem. Int. Ed., 2017, 56, 5994-6021.
[34]	Y. Huang, Z. Wang, H. Xiao, Q. Liu, X. Wang, J. Am. Chem. Soc., 2024, 146, 29006-29016.
[35]	W. Jiang, J. Wang, Y. Jiang, Y. Wu, B. Liu, X. Chu, C. Liu, G. Che, Y. Lu, J. Mater. Chem. A, 2023, 11, 2769-2779.
[36]	K. Jang, H. Yoon, J. S. Hyoung, D. S. A. Pratama, C. W. Lee, D.-W. Kim, Appl. Catal. B Environ., 2024, 341, 123327.
[37]	X. Hu, Z. Zhang, Z. Li, Y. Wu, W. Wei, Y. Wang, J. Xu, M. Ding, Appl. Catal. B, 2024, 358, 124445.
[38]	V.-H. Do, J.-M. Lee, Chem. Soc. Rev., 2024, 53, 2693-2737.
[39]	S. Geiger, O. Kasian, M. Ledendecker, E. Pizzutilo, A. M. Mingers, W.-T. Fu, O. Diaz-Morales, Z. Li, T. Oellers, L. Fruchter, A. Ludwig, K. J. J. Mayrhofer, M. T. M. Koper, S. Cherevko, Nat. Catal., 2018, 1, 508-515.
[40]	D. Guan, G. Ryu, Z. Hu, J. Zhou, C.-L. Dong, Y.-C. Huang, K. Zhang, Y. Zhong, A. C. Komarek, M. Zhu, X. Wu, C.-W. Pao, C.-K. Chang, H.-J. Lin, C.-T. Chen, W. Zhou, Z. Shao, Nat. Commun., 2020, 11, 3376.
[41]	T. Shinagawa, A. T. Garcia-Esparza, K. Takanabe, Sci. Rep., 2015, 5, 13801.
[42]	D. Antipin, M. Risch, Electrochem. Sci. Adv., 2023, 3, e2100213.
[43]	C. Wan, Y. Ling, S. Wang, H. Pu, Y. Huang, X. Duan, ACS Cent. Sci., 2024, 10, 658-665.
[44]	H. Yoon, B. Ju, D.-W. Kim, Battery Energy, 2023, 2, 20230017.
[45]	L. Giordano, B. Han, M. Risch, W. T. Hong, R. R. Rao, K. A. Stoerzinger, Y. Shao-Horn, Catal. Today, 2016, 262, 2-10.
[46]	H. Yoon, H. J. Song, J. S. Hyoung, S. W. Jung, A. Haryanto, C. W. Lee, D.-W. Kim, Appl. Catal. B, 2024, 358, 124382.
[47]	A. Grimaud, O. Diaz-Morales, B. Han, W. T. Hong, Y.-L. Lee, L. Giordano, K. A. Stoerzinger, M. T. M. Koper, Y. Shao-Horn, Nat. Chem., 2017, 9, 457-465.
[48]	S. Bhaskar, P. S. Dobal, S. B. Majumder, R. S. Katiyar, J. Appl. Phys., 2001, 89, 2987-2992.
[49]	S.-W. Chen, R. Villanneau, Y. Li, L.-M. Chamoreau, K. Boubekeur, R. Thouvenot, P. Gouzerh, A. Proust, Eur. J. Inorg. Chem., 2008, 2008, 2137-2142.
[50]	H. Yang, Y. Yang, S. Zou, J. Phys. Chem. B, 2006, 110, 17296-17301.
[51]	Y. Zhang, X. Gao, M. J. Weaver, J. Phys. Chem., 1993, 97, 8656-8663.
[52]	S. F. Parker, S. J. Robertson, S. Imberti, Mol. Phys., 2019, 117, 3417-3423.
[53]	Q. Sun, K. Reuter, M. Scheffler, Phys. Rev. B, 2004, 70, 235402.
[54]	X. Peng, Y. Lv, L. Fu, F. Chen, W. Su, J. Li, Q. Zhang, S. Zhao, RSC Adv., 2021, 11, 34095-34100.
[55]	A. Dey, G. Chandrabose, P. Ghosh, L. A. O. Damptey, A. H. Clark, V. Selvaraj, R. V. Kumar, N. St. J. Braithwaite, S. Zhuk, G. K. Dalapati, S. Ramakrishna, S. Krishnamurthy, Appl. Surf. Sci., 2021, 564, 150413.
[56]	J. H. Jung, Solid State Commun., 2005, 133, 103-107.
[57]	Y. Shi, L. Wang, M. Liu, Z. Xu, P. Huang, L. Liu, Y. Xu, Nat. Commun., 2025, 16, 909.
[58]	S. Xu, H. Liu, N. Zheng, H.-B. Tao, Adv. Mater. Interfaces, 2025, 12, 2400549.

通过铜诱导的表面重构动态调节钌催化剂中酸性析氧反应途径

Dynamic tuning of acidic oxygen evolution reaction pathways in Ru catalysts via Cu-induced surface restructuring

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