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氧化铱/氧化锰金属氧化物-载体相互作用实现了稳定的酸性水氧化。

IrO/MnO metal oxide-support interaction enables robust acidic water oxidation.

作者信息

Wang Fengge, Sui Jiaxi, Wang Zhen, Ling Shilin, Zhang Wei, Yan Yaotian, Qi Junlei, Luo Xiaoyan

机构信息

State Key Laboratory of Precision Welding & Joining of Materials and Structures, Harbin Institute of Technology, Harbin, China; Department of Energy and Environmental Materials, Suzhou Laboratory, 388 Ruoshui Road, Suzhou, China.

Department of Energy and Environmental Materials, Suzhou Laboratory, 388 Ruoshui Road, Suzhou, China.

出版信息

J Colloid Interface Sci. 2025 Apr;683(Pt 1):160-169. doi: 10.1016/j.jcis.2024.12.033. Epub 2024 Dec 6.

Abstract

The sluggish kinetics, poor stability, and high iridium loading in acidic oxygen evolution reaction (OER) present significant challenges for proton exchange membrane water electrolyzers (PEMWE). While supported catalysts can enhance the utilization and activity of Ir atoms, they often fail to mitigate the detrimental effects of over-oxidation and dissolution of Ir. Here, we leverage the redox properties of the Mn/Mn couple as electronic modulators to develop a low-iridium, durable electrocatalyst for acidic OER. Specifically, IrO nanoparticles are anchored onto MnO nanowires (denoted as IrO/MnO), through a molten salt-assisted synthesis method. This optimized IrO/MnO electrocatalyst features a substantially reduced iridium content and enhanced electronic structure due to strong metal-support interactions. Remarkably, the IrO/MnO catalyst demonstrates 7-fold increase in intrinsic activity and superior durability compared to commercial IrO. Both theoretical and experimental results indicate that dynamic electron transfer between Ir and Mn facilitates the rapid formation of highly oxidized iridium sites while simultaneously preventing excessive oxidation, thereby enhancing both the kinetics and stability for OER. A PEMWE utilizing IrO/MnO as the anode catalyst achieves 2000 mA cm @ 1.89 V without requiring supporting acidic electrolyte. Importantly, the PEMWE exhibits negligible degradation under harsh industrial operating conditions (1000 mA cm) with an Ir loading as low as 0.5 mg cm, while maintaining a low energy consumption of 45.58 kWh kg H corresponding to the green hydrogen production cost of $0.9 kg H, significantly lower than the 2026 US-DOE target, underscoring its potential for practical application.

摘要

在酸性析氧反应(OER)中,缓慢的动力学、较差的稳定性以及高铱负载量给质子交换膜水电解槽(PEMWE)带来了重大挑战。虽然负载型催化剂可以提高铱原子的利用率和活性,但它们往往无法减轻铱的过度氧化和溶解的有害影响。在此,我们利用Mn/Mn电对的氧化还原性质作为电子调节剂,开发了一种用于酸性OER的低铱、耐用的电催化剂。具体而言,通过熔盐辅助合成方法将IrO纳米颗粒锚定在MnO纳米线上(表示为IrO/MnO)。由于强金属-载体相互作用,这种优化的IrO/MnO电催化剂具有大幅降低的铱含量和增强的电子结构。值得注意的是,与商业IrO相比,IrO/MnO催化剂的本征活性提高了7倍,并且具有优异的耐久性。理论和实验结果均表明,Ir和Mn之间的动态电子转移促进了高氧化态铱位点的快速形成,同时防止过度氧化,从而提高了OER的动力学和稳定性。使用IrO/MnO作为阳极催化剂的PEMWE在1.89 V下可实现2000 mA cm,无需支持酸性电解质。重要的是,该PEMWE在苛刻的工业操作条件(1000 mA cm)下,铱负载低至0.5 mg cm时,降解可忽略不计,同时保持45.58 kWh kg H的低能耗,对应于0.9美元/kg H的绿色氢气生产成本,显著低于2026年美国能源部的目标,突出了其实际应用潜力。

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