在Fe-N-C单原子催化剂中由内在反应中间体诱导的自我调整活动
Yu Wang1, Yu-Jia Tang2, Kun Zhou1,2
1Environmental Process Modelling Centre, Nanyang Environment and Water Research Institute , Nanyang Technological University , 1 CleanTech Loop , Singapore 637141 , Singapore.
Journal of the American Chemical Society
|August 31, 2019
概括
Fe-N-C 单原子催化剂 (SAC) 显示出氧降解反应 (ORR) 的前景. 一个新的微动力学模型揭示了一个内在的中间体自我调整活跃的FeN4位点,优化催化以获得更好的ORR性能.
科学领域:
- 催化剂
- 材料科学
- 电化学
背景情况:
- Fe-N-C单原子催化剂 (SAC) 在氧降解反应 (ORR) 中具有高度活性.
- 准确的催化机制和预测潜力的偏差阻碍了理想的SAC的发展.
研究的目的:
- 使用第一原则计算,阐明Fe-N-C SAC的ORR机制.
- 研究内在中间体在催化过程中的作用.
- 为设计高性能SAC提供指导.
主要方法:
- 使用第一原理计算来开发Fe-N-C SAC的ORR微动力模型.
- 该模型分析了FeN4活性部位及其中间体的行为.
- 用部分电流密度分析来确定主导反应途径.
主要成果:
- 确定了一种自我调整机制,其中OH*中间体将FeN4活性部位改为Fe(OH) N4.
- 这种Fe(OH) N4部分优化了中间结合,导致理论半波电位为~0.88V.
- 发现关联性ORR途径在Fe-N-C,Mn-N-C和Co-N-C SAC的离散性途径上占主导地位.
结论:
- 内在中间体在单原子催化中起着至关重要的作用,必须考虑它们以准确阐明机制.
- 在Fe-N-C SAC中观察到的高ORR活性中,Fe-OH-N4活性位点是关键.
- 这项研究提供了用于能源应用的先进SAC的合理设计的见解.
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