铁3D轨道配置依赖电子转移,以实现高效的芬顿式催化
Yijie Wu1, Xin Wang2, Tiantian She1
1School of Environment, Jiangsu Engineering Lab of Water and Soil Eco-remediation, Nanjing Normal University, Nanjing, 210023, P. R. China.
Small (Weinheim an der Bergstrasse, Germany)
|September 2, 2023
概括
具有特定d轨道配置的铁催化剂激活过氧硫酸盐 (PMS) 用于水处理. 在ZnFe2O4中的八面体铁位点表现出更高的活性,并产生非激进反应性氧物种 (ROS),以有效地去除污染物.
科学领域:
- 材料科学 材料科学 材料科学
- 环境化学环境化学
- 催化剂是一种催化剂.
背景情况:
- 过渡金属是水处理中激活多氧硫酸盐 (PMS) 的关键.
- 了解控制PMS激活机制的电子结构至关重要,但具有挑战性.
- 螺旋铁矿为催化应用提供可调节的活性站点.
研究的目的:
- 为了研究d-轨道配置对铁位点 (八面体与四面体) 的影响,用于PMS激活.
- 为了将电子结构与催化活性和反应性氧物种 (ROS) 生成与四环素去除相关联.
- 为了阐明由不同铁协调环境激活PMS的反应机制.
主要方法:
- 合成具有明显铁d轨道配置的旋铁酸盐ZnFe2O4和FeAl2O4.
- 通过PMS激活去除四环素的催化活性的评估.
- 磁光谱分析以确定电荷,自旋状态和轨道排列.
- 灭实验以确定主要的ROS.
- 电化学测量和密度函数理论 (DFT) 计算.
主要成果:
- ZnFe2O4 (FeOh) 的特异活性 (136.58分−1F−1cm2) 比FeAl2O4 (FeTd) (97.47分−1F−1cm2) 的特异活性更高,用于四环素降解.
- 在ZnFe2O4中的FeOh位点优先产生单片氧 (1O2),而FeAl2O4中的FeTd位点产生超氧化基 (O2•−).
- 与FeTd相比,FeOh表现出优越的价值转换和界面电子转移能力.
- DFT的计算证实,八面体的d-轨道配置增强了Fe-O共价性,以实现高效的电子交换.
结论:
- 铁位点的d轨道配置显著影响PMS激活路径和效率.
- 在ZnFe2O4中的八面体Fe位点对PMS激活更有效,产生非激进的ROS和优异的催化性能.
- 本研究提供了基于d轨道配置的描述符,用于设计用于水处理的先进催化剂.
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