在水溶液中计算复查芬顿反应选择性和活性的pH和连接体依赖性
Ying Liu1, Peijun Hu1,2,3, Haifeng Wang1
1State Key Laboratory of Green Chemical Engineering and Industrial Catalysis, Centre for Computational Chemistry and Research Institute of Industrial Catalysis, East China University of Science and Technology, Shanghai 200237, China. hfwang@ecust.edu.cn.
Physical chemistry chemical physics : PCCP
|June 5, 2025
概括
芬顿反应是芬顿的反应.
科学领域:
- 环境化学环境化学
- 催化剂是一种催化剂.
- 计算化学的计算化学
背景情况:
- 芬顿反应对于废水处理至关重要,产生反应性氧化物种 (ROS),如基 (OH ̇) 和铁氧 (FeIVO2+).
- 在这些反应中ROS选择性的确切起源仍然是一个活跃的研究领域.
- 了解这些机制是优化水中的污染物降解的关键.
研究的目的:
- 为了研究原子级的芬顿反应机制,在水溶液中被FeIII-复合物催化.
- 量化反应性氧化物种 (ROS) 生产的活性和选择性.
- 阐明ROS选择性中的pH依赖开关和连接体效应的作用.
主要方法:
- 利用*ab initio*分子动力学来模拟原子层次的反应路径.
- 采用微动力学建模来量化反应速率和选择性.
- 研究了pH和连接体特性对中间稳定性和ROS形成的影响.
主要成果:
- 证明了ROS选择性的pH依赖开关:OH在pH<2.5时占主导地位,而FeIVO2+在pH>2.5时占主导地位.
- 表明Fe-复合体连接体通过改变OH中间体的结合强度来调节ROS的选择性和活性.
- 在异质FeOCl中的FeIIFeIII双位点确定了优化的OH结合,作为有效催化的关键.
结论:
- 提供了原子层面的洞察力,了解在芬顿催化过程中ROS的pH依赖性选择性.
- 突出了连接体设计在同质芬顿反应中控制ROS输出的重要作用.
- 进步了对均质和异质芬顿催化物的理解,以改善废水处理策略.
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