用轴向异原子 (P,S和Cl) 装饰的Fe单原子催化剂用于氧降解反应:DFT研究的一项研究
Qian Xue1,2, Xuede Qi1,2, Kun Li1
1College of Chemistry and Chemical Engineering, Chongqing University of Technology Chongqing 400054 China xqqi@cqut.edu.cn.
装饰FeN4单原子催化剂与P,S和Cl等轴向异原子调节它们的氧减少反应 (ORR) 活性. FeN4Cl显示出最佳性能,为设计先进的ORR电催化剂提供了一份指南.
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:
- 在石墨烯中嵌入FeN4的单原子催化剂 (SAC) 对氧降解反应 (ORR) 是有前途的.
- 通过装饰调节Fe活性部位可以进一步提高FeN4 SACs的性能.
研究的目的:
- 为了比较研究纯FeN4和轴向异原子装饰的FeN4 SACs (FeN4L,其中L=P,S,Cl) 的ORR活性.
- 调查轴向异原子装饰对FeN4 SACs反应路径和性能的影响.
主要方法:
- 用密度函数理论 (DFT) 的计算来研究FeN4和FeN4L SACs上的ORR机制.
- 对各种中间体的速度决定步骤 (RDS),超电位和吸附能量的分析.
主要成果:
- 纯FeN4的RDS是OH降解为H2O (超电位 = 0.58V).
- 对于FeN4L,RDS转向将O2减少为OH.
- FeN4Cl表现出最低的超电位 (0.51V),表明最高的ORR活动.
- 在FeN4L SACs的d带中心和ORR活动之间观察到火山关系.
结论:
- 轴向异原子装饰,特别是与Cl,通过减轻物种吸附,显著增强ORR活性.
- ΔG(*OH) 作为预测这些系统中ORR活动的描述符.
- 这项研究为设计电化学设备的优质ORR电催化剂提供了洞察力.
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