金属与氧的结合特性决定了RuO2和IrO2在酸氧演化反应中的活性和稳定性差异
Longdan Tang1,2, Xia Chen1,2, Zhuoyang Xie1,2
1State Key Laboratory of Advanced Chemical Power Sources (Chongqing University), Chongqing, 400044, China. liliracial@cqu.edu.cn.
Physical chemistry chemical physics : PCCP
|April 14, 2025
概括
二氧化卢和二氧化表现出不同的氧化演化反应 (OER) 行为. DFT计算显示RuO2更活跃,但不太稳定,而IrO2更稳定,但由于结合差异而不太活跃.
科学领域:
- 电化学 电化学 电化学
- 材料科学 材料科学 材料科学
- 计算化学计算化学
背景情况:
- 二氧化卢 (RuO2) 和二氧化 (IrO2) 是酸氧演化反应 (OER) 的关键电催化剂.
- 了解这些催化剂的内在活性-稳定性关系至关重要,但仍然具有挑战性.
研究的目的:
- 通过使用DFT在酸性介质中研究RuO2和IrO2之间的不同OER催化行为的起源.
- 建立电子结构,粘合性质和电催化性能之间的相关性.
主要方法:
- 密度函数理论 (DFT) 的计算被用来系统地研究RuO2和IrO2.
- 进行了机械分析和电子结构调查,以了解OER路径和稳定性.
主要成果:
- 通过吸附物演化机制,RuO2表现出更高的活性 (0.698V的较低超电位),但遭受RuO4^2-溶解.
- 由于具有更多的共价I-氧键,IrO2表现出增强的稳定性 (溶解能变化>2.9 eV),尽管超电位较高 (0.909 V).
- 在RuO2中的离子结合促进了中间溶解,但促进了溶解,而在IrO2中的共价结合以活动成本稳定了中间体.
结论:
- 结合性质从根本上决定了RuO2和IrO2在酸性OER中的活动稳定性权衡.
- 这项研究为设计先进的,酸稳定的OER电催化剂提供了洞察力,提高了性能.
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