对氧降解反应的金属-Fe@NC双原子催化剂的理论见解
Jianrui Zhang1, Ziwei Wang1, Yi Zhang2
1School of Chemistry, Engineering Research Center of Energy Storage Materials and Devices of Ministry of Education, National Innovation Platform (Center) for Industry-Education Integration of Energy Storage Technology, Xi'an Jiaotong University, Xi'an 710049, PR China.
用主要组元素修改铁碳催化剂破坏了电子对称性,显著增强了氧降解反应 (ORR) 活性. 这一战略为设计高效,非昂贵的ORR电催化剂提供了一个新的原则.
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) 单原子催化剂是氧降解反应 (ORR) 的有希望的非珍贵的电催化剂.
- 它们的活性受到Fe-N4部分对称电子结构的限制,阻碍了氧化中间体的可调性吸附.
研究的目的:
- 开发Fe-N-C催化剂的电子调制策略,通过将Fe-N4位点与主要组元素相合.
- 为了打破内在的电子对称性并提高ORR性能.
主要方法:
- 密度函数理论 (DFT) 的计算被用来研究14个Fe-M@NC催化剂 (M = s-和p-块元素).
- 进行了自由能量分析和电子结构计算,以了解催化机制和电子特性.
主要成果:
- 大多数主要组元素稳定了Fe-N4动机,并减少了ORR过量的潜力.
- Fe-In@NC 显示出一个低的ORR 超电位,为0.39 V.
- 确定OH*质子作为普遍电位决定的步骤.
- s/p-d轨道杂交调节的电荷分布和d频段中心.
结论:
- 将Fe-N4位点与主组元素相合有效地打破了电子对称性并增强了ORR活动.
- 一个新的电子描述符, Δεs/p→d,与ORR超电位线性相关,为催化剂设计提供可转移的原则.
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