Integrated design of iridium-based catalysts for proton exchange membrane water electrolyzers

doi:10.1016/S1872-2067(25)64787-5

Chinese Journal of Catalysis ›› 2025, Vol. 77: 20-44.DOI: 10.1016/S1872-2067(25)64787-5

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Integrated design of iridium-based catalysts for proton exchange membrane water electrolyzers

Jiahao Yang^a^,^b, Zhaoping Shi^a^,^b, Minhua Shao^d^,^e^,^f, Meiling Xiao^a^,^b^,^c^,^*(), Changpeng Liu^a^,^b^,^c^,^*(), Wei Xing^a^,^b^,^c^,^*()

^aState Key Laboratory of Electroanalytic Chemistry, Jilin Province Key Laboratory of Low Carbon Chemistry Power, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, Jilin, China
^bSchool of Applied Chemistry and Engineering, University of Science and Technology of China, Hefei 230026, Anhui, China
^cCIAC - HKUST Joint Laboratory for Hydrogen Energy, Changchun 130022, Jilin, China
^dDepartment of Chemical and Biological Engineering, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong 999077, China
^eCIAC-HKUST Joint Laboratory for Hydrogen Energy, Energy Institute, The Hong Kong University of Science and Technology, Clear Watery Bay, Kowloon, Hong Kong 999077, China
^fGuangzhou Key Laboratory of Electrochemical Energy Storage Technologies, Fok Ying Tung Research Institute, The Hong Kong University of Science and Technology, Guangzhou 511458, Guangdong, China

Received:2025-05-15 Accepted:2025-07-07 Online:2025-10-18 Published:2025-10-05
Contact: *E-mail: mlxiao@ciac.ac.cn (M. Xiao), liuchp@ciac.ac.cn (C. Liu), xingwei@ciac.ac.cn (W. Xing).
About author:Meiling Xiao received her PhD degree in physical chemistry from the Chinese Academy of Sciences in 2017. She worked at the University of Waterloo as a postdoc and joined Changchun Institute of Applied Chemistry in 2021 as a full professor. She was selected for the Special Talent Program B of CAS and the Outstanding Youth Foundation of Jilin Province. She has published over 40 papers in J. Am. Chem. Soc., Angew. Chem. Int. Ed., Adv. Mater., etc. with over 5100 citations, H-factor 33. Her research interests include single-atom heterogeneous catalysis, fuel cells, and water electrolyzers.
Changpeng Liu received his PhD in Physical Chemistry in 2002 and was appointed as a professor at the Changchun Institute of Applied Chemistry in 2012. He has successively presided over, undertaken, participated in, and completed several national and provincial-level scientific research projects. His research interests center on catalyst materials within the fuel cell and water electrolysis for hydrogen production systems, electrocatalysis and mass transfer processes, electrode interfaces, and membrane electrodes, the design and assembly of bipolar plate flow fields and fuel cell stacks, water, heat, and energy efficiency management, as well as the integration and application of system devices.
Wei Xing received his PhD in physical chemistry at the Changchun Institute of Applied Chemistry (CIAC) in 1995. He worked at the Hong Kong Productivity Council (HKPC), researching the electrochemical treatment of metal surfaces. In 2001, he joined the CIAC as a professor and devoted his work to the development of advanced chemical power sources. He has received several awards, including the Jilin Province Science and Technology Award, the Science and Technology Award from the Chemical Industry and Engineering Society of China. He has published over 300 papers in peer-reviewed journals and has applied for more than 50 patents. His research areas currently involve proton exchange membrane fuel cells and water electrolyzers from fundamental electro-catalytic processes to relevant stack/system assembly and testing.
Supported by:
National Key R&D Program of China(2022YFB4002000);National Natural Science Foundation of China(22232004);Strategic Priority Research Program of the Chinese Academy of Sciences(XDA0400301);Jilin Province Science and Technology Development Program(20240302002ZD);Jilin Province Science and Technology Development Program(20240101019JC);Jilin Province Science and Technology Development Program(20210502002ZP);Jilin Province Development and Reform Commission Program(2023C032-6)

Abstract

Abstract:

Proton exchange membrane water electrolysis (PEMWE) has garnered significant attention as a pivotal technology for converting surplus electricity into hydrogen for long-term storage, as well as for providing high-purity hydrogen for aerospace and high-end manufacturing applications. With the ongoing commercialization of PEMWE, advancing iridium-based oxygen evolution reaction (OER) catalysts remains imperative to reconcile stringent requirements for high activity, extended longevity, and minimized noble metal loading. The review provides a systematic analysis of the integrated design of iridium-based catalysts in PEMWE, starting from the fundamentals of OER, including the operation environment of OER catalysts, catalytic performance evaluation within PEMWE, as well as catalytic and dissolution mechanisms. Subsequently, the catalyst classification and preparation/characterization techniques are summarized with the focus on the dynamic structure-property relationship. Guided by these understandings, an overview of the design strategies for performance enhancement is presented. Specifically, we construct a mathematical framework for cost-performance optimization to offer quantitative guidance for catalyst design. Finally, future perspectives are proposed, aiming to establish a theoretical framework for rational catalyst design.

Key words: Proton exchange membrane water, electrolysis, Oxygen evolution reaction, Iridium-based catalyst, Integrated design, Cost-performance optimization

Jiahao Yang, Zhaoping Shi, Minhua Shao, Meiling Xiao, Changpeng Liu, Wei Xing. Integrated design of iridium-based catalysts for proton exchange membrane water electrolyzers[J]. Chinese Journal of Catalysis, 2025, 77: 20-44.

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Figures/Tables 19

Fig. 1. Costs associated with PEMWE. (a) Cost distribution of PEMWE. (b) Comparison of precious metal prices.

Fig. 2. Comparison of the setup frameworks between the three-electrode test system and the PEMWE test system. (a) Schematic diagram of the setup for the three-electrode test system. (b) Schematic diagram of the setup for the PEMWE test system.

Fig. 3. The operational environment of OER catalysts in PEMWE electrolyzers.

Fig. 4. Factors influencing the evaluation of iridium-based catalyst activity in PEMWE electrolyzers. (a) Catalyst loading of oxygen evolution catalysts on the membrane electrode. Reproduced with permission Ref. [39]. Copyright 2016, Elsevier. (b) Content of ionomer used in oxygen evolution catalysts. Reproduced with permission Ref. [40]. Copyright 2010, Elsevier. (c) Thickness of the proton exchange membrane. Reproduced with permission Ref. [41]. Copyright 2024, Elsevier. (d) The coating on the anode titanium felt. Reproduced with permission Ref. [42]. Copyright 2024, Elsevier. (e) Testing the temperature of the electrolyzers. Reproduced with permission Ref. [43]. Copyright 2015, Elsevier.

Fig. 5. Key factors affecting the stability evaluation of iridium-based catalysts in PEMWE. (a) Catalyst loading of oxygen evolution catalysts on the membrane electrode. Reproduced with permission Ref. [47]. Copyright 2024, The American Association for the Advancement of Science. (b) Thickness of the proton exchange membrane. Reproduced with permission Ref. [41]. Copyright 2024, Elsevier. (c) Bubble interference. Reproduced with permission Ref. [48]. Copyright 2024, Elsevier. (d) The coating on the anode titanium felt. Reproduced with permission Ref. [42]. Copyright 2024, Elsevier. (e) Poisoning effects of metal ions. Reproduced with permission Ref. [49]. Copyright 2024, Elsevier.

Fig. 6. Schematic diagram of the oxygen evolution reaction mechanism.

Fig. 7. Analysis of catalytic elementary reactions and dissolution reactions. (a) Free energy profile of the oxygen evolution reaction under the AEM pathway and its calculation method. (b) Linear constraint relationship under the AEM pathway. (c) Volcano curve of oxygen evolution activity under the AEM pathway. Reproduced with permission Ref. [56]. Copyright 2011, Wiley-VCH. (d) Possible dissolution reactions of iridium-based catalysts. Reproduced with permission Ref. [57]. Copyright 2018, Wiley-VCH.

Fig. 8. Iridium metal and its hydroxides and oxides. (a) Iridium metal. Reproduced with permission Ref. [64]. Copyright 2018, Springer Nature. (b) Iridium hydroxide. Reproduced with permission Ref. [65]. Copyright 2022, American Chemical Society. (c) Amorphous iridium oxide. Reproduced with permission Ref. [66]. Copyright 2024, Wiley-VCH. (d) Rutile-type iridium oxide. Reproduced with permission Ref. [67]. Copyright 2015, Wiley-VCH. (e) 3R-phase iridium oxide. Reproduced with permission Ref. [68]. Copyright 2021, Elsevier. (f) 1T-phase iridium oxide. Reproduced with permission Ref. [69]. Copyright 2021, Springer Nature.

Fig. 9. Doped Ir-based catalysts. (a) Ir0.7Ru0.3Ox catalyst. Reproduced with permission Ref. [86]. Copyright 2017, Elsevier. (b) Mn0.15Ir0.85O2-σ catalyst. Reproduced with permission Ref. [87]. Copyright 2025, Wiley-VCH. (c) Sr-IrOx catalyst. Reproduced with permission Ref. [88]. Copyright 2024, Wiley-VCH. (d) Nb0.05Ir0.95O2 catalyst. Reproduced with permission Ref. [89]. Copyright 2025, Wiley-VCH. (e) B-IrO2 catalyst. Reproduced with permission Ref. [90]. Copyright 2014, Royal Society of Chemistry. (f) Ti-IrOx/Ir catalyst. Reproduced with permission Ref. [91]. Copyright 2023, Elsevier.

Fig. 10. Supported Ir-based catalysts. (a) IrO2/TiO2 catalyst. Reproduced with permission Ref. [109]. Copyright 2024, Elsevier. (b) Ir/Nb2O5-x catalyst. Reproduced with permission Ref. [110]. Copyright 2022, Wiley-VCH. (c) Ir-ZrTaOx catalyst. Reproduced with permission Ref. [111]. Copyright 2023, Elsevier. (d) IrO2@TaOx@TaB catalyst. Reproduced with permission Ref. [112]. Copyright 2024, Wiley-VCH. (e) RIE-Ir/CeOx catalyst. Reproduced with permission Ref. [113]. Copyright 2025, The American Association for the Advancement of Science. (f) IrO2/MnO2 catalyst. Reproduced with permission Ref. [114]. Copyright 2025, Elsevier.

Fig. 11. The spillover of oxygen-containing species for supported Ir-based catalysts. (a) One of the two-site mechanisms. Reproduced with permission Ref. [116]. Copyright 2025, Wiley-VCH. (b) Reverse Spillover for oxygen-containing species. Reproduced with permission Ref. [117]. Copyright 2025, Wiley-VCH. (c) Forward Spillover for oxygen-containing species. Reproduced with permission Ref. [121]. Copyright 2025, Royal Society of Chemistry.

Fig. 12. Multicomponent catalysts with special crystal structures. (a) KIr4O8 catalyst. Reproduced with permission Ref. [122]. Copyright 2024, Wiley-VCH. (b) Crystal structures of single and double perovskites. Reproduced with permission Ref. [126]. Copyright 2020, Wiley-VCH. (c) SrTi0.25Ir0.75O? catalyst. Reproduced with permission Ref. [127]. Copyright 2025, Elsevier. (d) Sr2CaIrO6 catalyst. Reproduced with permission Ref. [128]. Copyright 2022, Springer Nature.

Fig. 13. Special morphological structures. (a) Hollow IrOx nanospheres. Reproduced with permission Ref. [129]. Copyright 2025, Wiley-VCH. (b) Au-doped IrO2 nanoribbons. Reproduced with permission Ref. [100]. Copyright 2025, Royal Society of Chemistry. (c) Highly porous Ir0.7Ru0.3O2. Reproduced with permission Ref. [130]. Copyright 2019, Wiley-VCH. (d) HxIrOy nanosheets. Reproduced with permission Ref. [131]. Copyright 2025, Wiley-VCH. (e) Woodpile-structured Ir. Reproduced with permission Ref. [132]. Copyright 2020, Springer Nature.

Fig. 14. Common preparation methods for iridium-based catalysts.

Fig. 15. Common characterization techniques for oxygen evolution catalysts: (a) Three-electrode testing. Reproduced with permission Ref. [148]. Copyright 2019, American Chemical Society. (b) PEMWE electrolyzers testing. Reproduced with permission Ref. [153]. Copyright 2020, Elsevier. (c) XRD testing. Reproduced with permission Ref. [122]. Copyright 2024, Wiley-VCH. (d) Morphological structure-related testing. Reproduced with permission Ref. [154]. Copyright 2019, Elsevier. (e) XPS testing. Reproduced with permission Ref. [155]. Copyright 2011, Royal Society of Chemistry. (f) XAFS testing. Reproduced with permission Ref. [156]. Copyright 2018, Springer Nature.

Fig. 16. Emerging in-situ characterization techniques for oxygen evolution catalysts. (a) In-situ DEMS analysis. Reproduced with permission Ref. [159]. Copyright 2021, Elsevier. (b) In-situ IR spectroscopy. Reproduced with permission Ref. [160]. Copyright 2025, Wiley-VCH. (c) In-situ XRD analysis. Reproduced with permission Ref. [161]. Copyright 2023, Springer Nature. (d) In-situ XPS. Reproduced with permission Ref. [162]. Copyright 2014, Wiley-VCH. (e) In-situ XAFS spectroscopy. Reproduced with permission Ref. [163]. Copyright 2019, American Chemical Society. (f) In-situ Raman spectroscopy. Reproduced with permission Ref. [164]. Copyright 2021, American Chemical Society. (g) In-situ TEM. Reproduced with permission Ref. [128]. Copyright 2022, Springer Nature.

Fig. 17. A mathematical framework for low-iridium catalyst design. (a) Iridium loading analysis in anode catalysts. (b) Driving voltage analysis of PEMWE cells under conventional testing conditions (80 °C, 1 atm). (c) Correlation analysis between iridium loading and driving voltage. (d) Intrinsic property parameters of iridium-based catalysts in formulas linking driving voltage and iridium loading.

Fig. 18. Activity regulation strategies for oxygen evolution catalysts in PEMWE electrolyzers. (a) Optimization of adsorption energy of active sites in the AEM pathway. Reproduced with permission Ref. [166]. Copyright 2025, Springer Nature. (b) Promotion of the LOM pathway. Reproduced with permission Ref. [167]. Copyright 2024, Wiley-VCH. (c) Promotion of the oxygen evolution pathway (OPM). Reproduced with permission Ref. [168]. Copyright 2025, American Chemical Society. (d) Increase in the number of active sites. Reproduced with permission Ref. [169]. Copyright 2024, Wiley-VCH. (e) Maintaining the high conductivity of the catalyst. Reproduced with permission Ref. [170]. Copyright 2024, American Chemical Society.

Fig. 19. Stability regulation strategies for oxygen evolution catalysts in PEMWE electrolyzers. (a) Assessing the intrinsic stability of elements through Pourbaix diagrams. Reproduced with permission Ref. [172]. Copyright 2020, American Chemical Society. (b) Determining the structural stability of catalysts by calculating the formation energy of oxygen vacancies. Reproduced with permission Ref. [87]. Copyright 2025, Wiley-VCH. (c) Design strategies based on compositional effects. Reproduced with permission Ref. [173]. Copyright 2024, Wiley-VCH. (d) Design strategies based on anchoring effects. Reproduced with permission Ref. [146]. Copyright 2023, Springer Nature. (e) Design strategies based on hydroxylation effects. Reproduced with permission Ref. [174]. Copyright 2024, Springer Nature. (f) Design strategies based on self-healing effects. Reproduced with permission Ref. [175]. Copyright 2025, Wiley-VCH.

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Integrated design of iridium-based catalysts for proton exchange membrane water electrolyzers

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