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As the anode reaction of proton exchange membrane water electrolysis (PEMWE), the acidic oxygen evolution reaction (OER) is one of the main obstacles to the practical application of PEMWE due to its sluggish four-electron transfer process. The development of high-performance acidic OER electrocatalysts has become the key to improving the reaction kinetics. To date, although various excellent acidic OER electrocatalysts have been widely researched, Ir-based nanomaterials are still state-of-the-art electrocatalysts. Hence, a comprehensive and in-depth understanding of the reaction mechanism of Ir-based electrocatalysts is crucial for the precise optimization of catalytic performance. In this review, the origin and nature of the conventional adsorbate evolution mechanism (AEM) and the derived volcanic relationship on Ir-based electrocatalysts for acidic OER processes are summarized and some optimization strategies for Ir-based electrocatalysts based on the AEM are introduced. To further investigate the development strategy of high-performance Ir-based electrocatalysts, several unconventional OER mechanisms including dual-site mechanism and lattice oxygen mediated mechanism, and their applications are introduced in detail. Thereafter, the active species on Ir-based electrocatalysts at acidic OER are summarized and classified into surface Ir species and O species. Finally, the future development direction and prospect of Ir-based electrocatalysts for acidic OER are put forward.
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http://dx.doi.org/10.1002/smll.202403845 | DOI Listing |
Nat Commun
September 2025
State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun, China.
The dynamic reconstruction of oxygen evolution electrocatalysts dictates their performance, yet conventional Ir-based materials face an inherent activity-stability trade-off due to surface amorphization into hydrous IrO phases accompanied by lattice oxygen mechanisms. Here, we uncover a distinct reconstruction pathway for supported Ir nanoparticles, where a TiO@Ti substrate drives a bulk phase transition from metallic Ir to crystalline rutile IrO during electrocatalysis. Unlike surface-limited amorphization, this support-guided crystallization shifts the reaction mechanism from involving lattice oxygen mechanism to the complete adsorbate evolution mechanism, as confirmed by mechanistic and structural analyses.
View Article and Find Full Text PDFACS Nano
August 2025
Nanomaterials Centre, School of Chemical Enginering and Australian Institute for Bioengineering and Nanotechnology, The University of Queensland, St Lucia QLD 4072, Australia.
The Sabatier principle, which optimizes electrocatalyst design by balancing intermediate adsorption and desorption, typically manifests as a volcano trend in catalytic activity. Here, we introduce a hydrogen-bond-induced Sabatier phenomenon that enables the design of highly efficient Ir-based electrocatalysts. The optimized amorphous IrO catalyst achieves a high mass activity of 1741 A g, a 27-fold improvement over commercial IrO (64 A g), alongside a durability (S-number: 1.
View Article and Find Full Text PDFAdv Mater
July 2025
College of Polymer Science and Engineering, National Key Laboratory of Advanced Polymer Materials, Sichuan University, Chengdu, 610065, China.
Iridium (Ir), with optimal hydrogen binding energy (HBE) and hydroxyl bonding energy (OHBE), is considered a promising platform for achieving bi-directional hydrogen catalysis. However, traditional Ir-based catalysts with multiple crystalline facets exhibit a gap between the apparent activity and theoretical value, especially for the hydrogen oxidation reaction (HOR). Here, a molten co-growth process of Ir and vanadium nitride (Ir-VN) is reported, realizing precise exposure of lattice-matched Ir (111) on VN with optimal HBE and OHBE, for highly active hydrogen catalysis.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
July 2025
Key Laboratory of Precision and Intelligent Chemistry, School of Chemistry and Materials Science, University of Science and Technology of China, Hefei, Anhui, P.R. China.
The synthesis of sub-nanoscale noble metal catalysts is pivotal for enhancing electrocatalytic performance, yet achieving precise control over particle size at this scale remains a critical challenge. In this work, we propose a hierarchical confinement strategy which combines spatial confinement at nanoscale and anchoring confinement at atomic scale, to overcome the size limitations imposed by high-temperature sintering. Using this strategy, a series of uniformly sized (∼1 nm) Ir-based alloy clusters, including IrMn, IrFe, IrCo and IrNi, are successfully fabricated.
View Article and Find Full Text PDFAdv Mater
June 2025
Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai, 201210, China.
Achieving high activity and stability while minimizing Ir usage poses a significant challenge in the industrialization of proton exchange membrane water electrolysis (PEMWE). Herein we report a sulfur-doping strategy that enables the OER pathway on IrO nanoparticles (IrO/S) to switch from conventional adsorption evolution mechanism (AEM) to lattice oxygen mechanism (LOM) while maintaining Ir─O bond stability, thus achieving a significant enhancement in both intrinsic activity and durability. Advanced spectroscopies and theoretical calculations reveal that the Ir─S coordination motif within the lattice increases the electron density of the Ir center and enhances Ir─O covalency, thus triggering the LOM pathway.
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