附近的原子环境对Fe-N-C催化剂对氧减少反应的影响:基于密度函数理论的研究研究
PengFei Yuan1, Chong Li2, Jiannan Zhang3
1Shandong Laboratory of Yantai Advanced Materials and Green Manufacturing, Yantai 265503, China. pfyuan@amgm.ac.cn.
Physical chemistry chemical physics : PCCP
|February 7, 2024
概括
Fe-N-C催化剂对燃料电池具有前景,但Fe-N4位点附近的原子结构是关键. 这项研究确定了增强氧降解反应 (ORR) 活性的最佳原子配置.
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--碳 (Fe-N-C) 材料是聚合物电解质膜燃料电池中氧降解反应 (ORR) 的主要非贵金属催化剂.
- 优化Fe-N4活性部位周围的原子环境对于提高催化剂性能至关重要.
- 了解邻近原子对催化活性的影响仍然是一个重大挑战.
研究的目的:
- 用计算方法研究Fe-N4地点附近的原子配置对ORR活动的影响.
- 确定特定的原子结构,最大限度地提高ORR的限制潜力.
- 阐明控制Fe-N-C催化剂活动的电子结构原理.
主要方法:
- 密度函数理论 (DFT) 的计算被用来分析吉布斯自由能量.
- 计算电极 (CHE) 模型被用来确定反应能量.
- 进行了电子结构分析和恒定电位计算.
主要成果:
- 在Fe-N4位点附近的两个C-O-C原子结构 (str-11) 被确定为具有最高的限制潜力 (0.813 V).
- 周围的邻近的碳原子对O-doped结构中的限制潜力表现出不同的敏感性 (A型和B型).
- 最佳ORR活动与Fe d轨道对带最大值 (VBM) 在玛点的贡献相关.
结论:
- 在酸性 (pH 1 的0.695 V) 和性 (pH 14 的0.926 V) 条件下,str-11结构表现出极好的ORR性能.
- 微动力学模拟表明,str-11在操作条件下,特别是性介质中,是ORR的可行的活性部位.
- 这项工作通过控制Fe-N4站点的原子环境,为设计高性能Fe-N-C催化剂提供了关键的见解.
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