旋转交叉和交换对氧进化反应的影响,由双金属金属有机框架催化
Guangsheng Liu1, Feng Xie2, Xu Cai3
1Department of Chemistry and Biochemistry, Duquesne University, Pittsburgh, Pennsylvania 15282, United States.
ACS catalysis
|June 13, 2024
概括
双金属金属有机框架 (BMOFs) 显示了增强的氧化演化反应 (OER) 性能. 基于NiFe的BMOF表现出优越的OER动力学和热力学,这是由于协同的双金属效应和更好的导电性.
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
- 计算化学的计算化学
背景情况:
- 双金属金属有机框架 (BMOFs) 展示了由于双金属协同效应的氧化演化反应 (OER) 性能有前途.
- 在OER中这些双金属协同作用的精确机制仍然不完全理解.
研究的目的:
- 使用密度函数理论系统地研究基于NiAl和NiFe的BMOF的OER性能.
- 阐明自旋状态,外部潜力和pH对OER能量和动力学的作用.
主要方法:
- 密度函数理论 (DFT) 的计算被用来检查中间体的所有旋转状态.
- 恒定电位和电化学推动弹性带方法被用来绘制自由能量障碍的地图.
- 对于NiAl和NiFeBMOFs,在不同的外部潜力和pH下考虑了旋转交叉效应.
主要成果:
- 具有浅孔陷和较高Ni氧化状态的旋转状态促进OER.
- 外部潜力诱导的旋转交叉显著改变了反应和激活能.
- 与NiAl BMOF相比,NiFe BMOF表现出优越的OER热力学和动力学.
- 由于Ni-Fe的协同效应,NiFe BMOF的电导率提高提高了OER动力学.
结论:
- 由于有利的旋转状态,减少带间隙和通过Ni-Fe相互作用提高导电性,NiFe BMOF具有增强的OER性能.
- DFT的结果与实验性的OER偏振曲线和Tafel图表一致,验证了这些发现.
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