Zr-Doped Ru-Based Catalyst for Highly Active and Durable Acidic Oxygen Evolution Reaction

Abstract

Developing an oxygen evolution reaction catalyst that exhibits both high catalytic activity and robust stability in acidic media remains a significant challenge to date. In this work, a RuZrOx/Ti-1 catalyst was successfully constructed on a Ti mesh substrate via a facile one-step pyrolysis method. Physical characterization reveals that the as-prepared RuZrOx/Ti-1 catalyst exhibits a densely packed nanosphere morphology on its surface, accompanied by abundant pores, which can provide a rich interface for the oxygen evolution reaction. The RuZrOx/Ti-1 catalyst achieves a low overpotential of only 199 mV for the OER at a current density of 10 mAꞏcm⁻² and demonstrates excellent long-term durability, operating stably for 400 h at this current density. In summary, this work provides a viable strategy for designing high-performance acidic OER catalysts, thereby paving the way for the advancement of electrodes for water oxidation.

Keywords

Acidic oxygen evolution reaction (OER) / Zr doping / Ru-based electrocatalyst

References

[1] Jiao J, Chen D, Zhao H, Dong Y, Mu S. Durable ruthenium oxide catalysts for water oxidation reaction.Sci. China Chem. 2025, 68, 2217-2233. DOI:10.1007/s11426-024-2227-2

[2] Xu H-M, Zhu H-R, Huang C-J, Zhang Z-J, Shuai T-Y, Zhan Q-N, et al. Recent advances in Fe-N-C- and Co-N-C-based materials as bifunctional electrocatalysts for oxygen reduction and oxygen evolution. Sci. China Chem. 2024, 67, 1137-1160. DOI:10.1007/s11426-023-1863-8

[3] Tockhorn P, Sutter J, Cruz A, Wagner P, Jäger K, Yoo D, et al. Nano-optical designs for high-efficiency monolithic perovskite-silicon tandem solar cells. Nat. Nanotechnol. 2022, 17, 1214-1221. DOI:10.1038/s41565-022-01228-8

[4] Zhao S, Yang Y, Tang Z. Insight into Structural Evolution, Active Sites, and Stability of Heterogeneous Electrocatalysts. Angew. Chem. Int. Ed. 2022, 61, e202110186. DOI:10.1002/anie.202110186

[5] Yang Y, Gao H, Zhu C, Sun W, Zeng J, Wang X, et al. Enriching Edge-Structures of NiFe-LDH via Ru-Ni Site Interchange as Efficient and Stable OER Catalytic Electrodes. Adv. Funct. Mater. 2026, 36, e14599. DOI:10.1002/adfm.202514599

[6] Aboelazm E, Thalji MR, Hamid MA, Park H, Zuhaib H, Khe CS, et al. d-p-d orbital coupling-driven electronic modulation in CoSe₂/TiSe₂@Ti₃C₂T_x MXene for enhanced supercapacitors and oxygen evolution reaction. Chem. Eng. J. 2026, 528, 172358. DOI:10.1016/j.cej.2025.172358

[7] Wang E, Luo L, Feng Y, Wu A, Li H, Luo X, et al. Ultrafine orderedL1₂-Pt-Co-Mn ternary intermetallic nanoparticles as high-performance oxygen-reduction electrocatalysts for practical fuel cells. J. Energy Chem. 2024, 93, 157-165. DOI:10.1016/j.jechem.2024.01.054

[8] Zhao W, Chi B, Liang L, Yang P, Zhang W, Ge X, et al. Optimizing the Electronic Structure of Ordered Pt-Co-Ti Ternary Intermetallic Catalyst to Boost Acidic Oxygen Reduction. ACS Catal. 2022, 12, 7571-7578. DOI:10.1021/acscatal.2c00554

[9] She L, Zhao G, Ma T, Chen J, Sun W, Pan H. On the Durability of Iridium-Based Electrocatalysts toward the Oxygen Evolution Reaction under Acid Environment. Adv. Funct. Mater. 2022, 32, 2108465. DOI:10.1002/adfm.202108465

[10] Liu M, Zhang Y-Q, Wang X, Lang F, Li N, Bu X-H. Recent advances in metal-organic frameworks for oxygen evolution reaction electrocatalysts. Sci. China Chem. 2023, 66, 2754-2779. DOI:10.1007/s11426-023-1725-8

[11] Zhou D, Chang Y, Tang J, Ou P. Mn_0.75Ru_0.25O₂ with Low Ru Concentration for Active and Durable Acidic Oxygen Evolution. Small 2025, 21, 2412265. DOI:10.1002/smll.202412265

[12] Cherevko S, Geiger S, Kasian O, Kulyk N, Grote J-P, Savan A, et al. Oxygen and hydrogen evolution reactions on Ru, RuO₂, Ir, and IrO₂ thin film electrodes in acidic and alkaline electrolytes: A comparative study on activity and stability. Catal. Today 2016, 262, 170-180. DOI:10.1016/j.cattod.2015.08.014

[13] Ying J, Chen J-B, Xiao Y-X, Cordoba de Torresi SI, Ozoemena KI, Yang X-Y. Recent advances in Ru-based electrocatalysts for oxygen evolution reaction. J. Mater. Chem. A 2023, 11, 1634-1650. DOI:10.1039/D2TA07196G

[14] Xu X, Jo YH, Yu T. Facile synthesis of ultra-small Ru/NiO hybrid nanoparticles anchored on carbon nanotubes for enhanced bifunctional OER and HER performance. Int. J. Hydrogen Energy 2026, 208, 153543. DOI:10.1016/j.ijhydene.2026.153543

[15] Yang W, Jia L, Cao J, Miao Y, Mei B, Ouyang R, et al. Lanthanides Regulate the Oxide Pathway Mechanism of RuO₂ to Boost Acidic Oxygen Evolution. Nano Lett. 2026, 26, 3873-3881. DOI:10.1021/acs.nanolett.6c00082

[16] Wang J, Cheng C, Yuan Q, Yang H, Meng F, Zhang Q, et al. Exceptionally active and stable RuO₂ with interstitial carbon for water oxidation in acid. Chem 2022, 8, 1673-1687. DOI:10.1016/j.chempr.2022.02.003

[17] Chang J, Shi Y, Wu H, Yu J, Jing W, Wang S, et al. Oxygen Radical Coupling on Short-Range Ordered Ru Atom Arrays Enables Exceptional Activity and Stability for Acidic Water Oxidation. J. Am. Chem. Soc. 2024, 146, 12958-12968. DOI:10.1021/jacs.3c13248

[18] Wang J, Yang H, Li F, Li L, Wu J, Liu S, et al. Single-site Pt-doped RuO₂ hollow nanospheres with interstitial C for high-performance acidic overall water splitting. Sci. Adv. 2022, 8, eabl9271. DOI:10.1126/sciadv.abl9271

[19] Zhang D, Li M, Yong X, Song H, Waterhouse GIN, Yi Y, et al. Construction of Zn-doped RuO₂ nanowires for efficient and stable water oxidation in acidic media. Nat. Commun. 2023, 14, 2517. DOI:10.1038/s41467-023-38213-1

[20] Wei D, Liu TM, He YH, Wei BY, Pan JH, Zhang JW, et al. Corrigendum: Radical 1,4/5-Amino Shift Enables Access to Fluoroalkyl-Containing Primary β(γ)-Aminoketones under Metal-Free Conditions. Angew. Chem. Int. Ed. 2021, 60, 26020. DOI:10.1002/anie.202114499

[21] Ospina-Acevedo F, Albiter LA, Bailey KO, Godínez-Salomón JF, Rhodes CP, Balbuena PB. Catalytic Activity and Electrochemical Stability of Ru_1−xM_xO₂ (M = Zr, Nb, Ta): Computational and Experimental Study of the Oxygen Evolution Reaction. ACS Appl. Mater. Interfaces 2024, 16, 16373-16398. DOI:10.1021/acsami.4c01408

[22] Zhang H-Z, Wang X, Xie Y-F, Li C, Zhao Z-G, Shao P-Y, et al. Weakening the RuO covalency to promote the dominance of adsorbate evolution mechanism pathway by zirconium doping for ultra-stable proton exchange membrane water electrolysis. J. Colloid Interface Sci. 2026, 703, 139091. DOI:10.1016/j.jcis.2025.139091

[23] Wang W, Li Y, Wang J, Xiao R, Liu K, Song X, et al. Interfacial electron redistribution through the Ru-N-Fe bond to stabilize high-valence metal sites for efficient electrocatalytic oxygen evolution.Renew. Energy 2025, 244, 122656. DOI:10.1016/j.renene.2025.122656

[24] Bayatsarmadi B, Zheng Y, Tang Y, Jaroniec M, Qiao S-Z. Significant Enhancement of Water Splitting Activity of N-Carbon Electrocatalyst by Trace Level Co Doping.Small 2016, 12, 3703-3711. DOI:10.1002/smll.201601131

[25] Abdul M, Jiang X, Alotaibi NH, Mohammad S, Rahman AU, Jing B, et al. Synergistic improvement of OER/HER electrocatalytic performance of Cu₂Te via the introduction of Zr for water electrolysis. Int. J. Hydrogen Energy 2025, 128, 329-341. DOI:10.1016/j.ijhydene.2025.04.259

[26] Huang Y, Zhou T, Hu Y, Yang Y, Yang F, Huang W, et al. Ordered derivatives on Ti surface enhance the OER activity and stability of Ru-based film electrode. Int. J. Hydrogen Energy 2023, 48, 33411-33421. DOI:10.1016/j.ijhydene.2023.05.108

[27] Zhang X-Y, Yin H, Dang C-C, Nie H, Huang Z-X, Zheng S-H, et al. Unlocking Enhanced Catalysis Stability in Acidic Oxygen Evolution: Structural Insights for PEM Applications under High-Current Density. Angew. Chem. Int. Ed. 2025, 64, e202425569. DOI:10.1002/anie.202425569

[28] Wang X, Wang J, Xu R, Yang L. Boosting the electrocatalytic performance of Co₂P/Ni₃S₂ heterostructure for efficient water splitting. Int. J. Hydrogen Energy 2024, 91, 683-692. DOI:10.1016/j.ijhydene.2024.10.205

[29] Xu N, Li M-M, Sun H-Y, Li G, Wen X, Ouyang D, et al. Atmosphere-driven oriental regulation of Ru valence for boosting alkaline water electrolysis. Chem. Eng. J. 2024, 502, 158051. DOI:10.1016/j.cej.2024.158051

[30] Zhou F, Chen J, Yang Y, Ke X, Liu X, Zhang L, et al. Exceptionally active and stable RuO₂ by constructing p-n heterojunction between Co₃O₄ and RuO₂ for acidic water oxidation. Appl. Surf. Sci. 2023, 641, 158508. DOI:10.1016/j.apsusc.2023.158508

[31] Wang G, Wan W, Chen M, Li J, Wu X, Huang S, et al. Building strong metal-support interaction between TiN and RuO₂ for efficient acidic oxygen evolution reaction. Int. J. Hydrogen Energy 2024, 71, 804-810. DOI:10.1016/j.ijhydene.2024.05.315

[32] Yang G, Zhu B, Fu Y, Zhao J, Lin Y, Gao D, et al. High-valent Zirconium-doping modified Co₃O₄ weave-like nanoarray boosts oxygen evolution reaction. J. Alloys Compd. 2021, 886, 161172. DOI:10.1016/j.jallcom.2021.161172

[33] Bao J, Zhang X, Fan B, Zhang J, Zhou M, Yang W, et al. Ultrathin Spinel-Structured Nanosheets Rich in Oxygen Deficiencies for Enhanced Electrocatalytic Water Oxidation. Angew. Chem. Int. Ed. 2015, 54, 7399-7404. DOI:10.1002/anie.201502226

[34] Gao J, Xu C-Q, Hung S-F, Liu W, Cai W, Zeng Z, et al. Breaking Long-Range Order in Iridium Oxide by Alkali Ion for Efficient Water Oxidation. J. Am. Chem. Soc. 2019, 141, 3014-3023. DOI:10.1021/jacs.8b11456

[35] Xiao PW, Zhang ZF, Ge JJ, Deng YL, Chen XF, Zhang JR, et al. Surface passivation of intensely luminescent all-inorganic nanocrystals and their direct optical patterning. Nat. Commun. 2023, 14, 49. DOI:10.1038/s41467-022-35702-7

[36] Sun L, Feng M, Peng Y, Zhao X, Shao Y, Yue X, et al. Constructing oxygen vacancies by doping Mo into spinel Co₃O₄ to trigger a fast oxide path mechanism for acidic oxygen evolution reaction. J. Mater. Chem. A 2024, 12, 8796-8804. DOI:10.1039/D4TA00655K

[37] Wang H, Wen T, Gong X, Ren M, Tang Q, Hu A, et al. Ta-doped charge-transferring Ir shells on Ru cores: Dual stabilisation and synergistic OER catalysis for PEMWE. Chem. Commun. 2026, 62, 6586-6590. DOI:10.1039/D6CC00726K

[38] Li L, Zhao J, Song Y, Li C, Zeng X, Chen L, et al. Synthesis of highly active oxygen evolution reaction electrocatalysts using balsa woods. Mater. Lett. 2024, 357, 135744. DOI:10.1016/j.matlet.2023.135744

[39] Zhang J, Qin H, Cao X, Jia W, Ma R, Chen X, et al. Constructing Adjustable Heterointerface for Enhancing Acidic Oxygen Evolution Performances of RuO₂@CoMnO₃ Nanosheets Electrocatalysts. ACS Mater. Lett. 2024, 6, 3016-3024. DOI:10.1021/acsmaterialslett.4c00778

[40] Yang S, Wang Y, Gong Y. Anchoring ruthenium single atoms into the carbon nanotubes-supported nickel-based sulfides for enhanced electrocatalytic oxygen evolution. J. Colloid Interface Sci. 2025, 699, 138255. DOI:10.1016/j.jcis.2025.138255

[41] Li L, Zhang G, Zhou C, Lv F, Tan Y, Han Y, et al. Lanthanide-regulating Ru-O covalency optimizes acidic oxygen evolution electrocatalysis. Nat. Commun. 2024, 15, 4974. DOI:10.1038/s41467-024-49281-2

[42] Yuan B, Dang Q, Liu H, Sendeku MG, Peng J, Fan Y, et al. Synergistic niobium and manganese co-doping into RuO₂ nanocrystal enables PEM water splitting under high current. Nat. Commun. 2025, 16, 4583. DOI:10.1038/s41467-025-59710-5

[43] Chen Y, Liu Y, Li L, Sakthive T, Guo Z, Dai Z. Asymmetric Bond Delta-Polarization at the Interfacial Se-Ru-O Bridge for Efficient pH-Robust Water Electrolysis. Adv. Funct. Mater. 2024, 34, 2406587. DOI:10.1002/adfm.202406587