铁的β-氧化对于氧气演化反应的强烈面部依赖性活性
Ananth Govind Rajan1,2, John Mark P Martirez3, Emily A Carter2,3,4
1Department of Chemical Engineering, Indian Institute of Science, Bengaluru, Karnataka 560012, India. ananthgr@iisc.ac.in.
Physical chemistry chemical physics : PCCP
|May 8, 2024
概括
用铁添加的氧化 (β-NiOOH) 显示出水分的潜力,但其活性取决于铁.
科学领域:
- 材料科学 材料科学 材料科学
- 电化学 电化学 电化学
- 计算化学计算化学
背景情况:
- 铁 (Fe) 化β-氧化 (β-NiOOH) 是氧化演化反应 (OER) 的关键电催化剂.
- 了解Fe剂如何影响β-NiOOH中的OER活性对于提高水分效率至关重要.
- 氧化演化反应 (OER) 是电化学水分的瓶,用于可持续的生产.
研究的目的:
- 在其最稳定的晶体学方面研究化β-NiOOH的OER活性.
- 阐明Fe补充剂调节β-NiOOH电氧化活性的机制.
- 为了确定Fe协调和氧化还原活性在Fe化β-NiOOH的OER性能中的作用.
主要方法:
- 利用混合密度函数理论 (DFT) 和哈伯德纠正的DFT.
- 研究了β-NiOOH的热力学上有利的 (0001) 和 (101̄0) 晶体学方面.
- 在OER氧化回氧循环期间涉及过渡金属中心氧化和减少的被认为是活性位点.
主要成果:
- 六倍格子协调的Fe是氧化还原不活的,而五倍协调的Fe则表现出氧化还原活性.
- 在大多数研究地点 (oxo,hydroxo,hydrated) 上,Fe兴奋剂只会对OER过量的潜力产生微不足道的影响.
- 在 (101̄0) 面 (0.52 V从0.86 V) 上的五倍协调氧位点上观察到超电位的显著下降.
结论:
- 未使用的β-NiOOH表现出面独立的OER活性,但用Fe的β-NiOOH活性高度依赖面.
- 只有具有四倍格子协调的Fe位点的侧面被预测为杂材料活跃.
- 建议选择性增长具有低Fe协调数的方面,以增强水分裂活动.
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