Collaborative Research: Synergistic Actions of Peroxy Acids and Metals for Advanced Water Treatment: Delineating Multi-Oxidant Mechanisms

在美国国家科学基金会化学部环境化学科学项目的支持下，格鲁吉亚理工学院的黄清华教授和德克萨斯农工大学的Virender Sharma教授将研究涉及过氧酸（POA）和金属的多氧化剂系统在水处理中的应用。 POA、高铁酸盐（VI）和高锰酸盐（VII）是公认的氧化剂，但每种都显示出一些局限性。该项目将探索POA与高价金属（HVM）或低价金属（LVM）离子在多氧化剂系统中的组合，该系统可以降解水处理中的污染物并激活有机合成中的化学键。本项目旨在阐明基本的反应动力学和机制，以最大限度地发挥应用潜力。此外，该项目将加强教育，扩大代表性不足群体的参与。实例活动包括通过与格鲁吉亚和得克萨斯州的九个少数民族机构建立伙伴关系，教授和招募少数民族学生参加研究，以及教授K-12 STEM（科学、技术、工程和数学）教师。POA与高价金属（HVM）（例如，高铁酸盐（VI）和高锰酸盐（VII））或低价金属（LVM）（例如，Fe（II）和Mn（II）物种可以显著增强水污染物的降解。POA基自由基和中间高价金属氧代物质（例如，Fe（V，IV）=O，Mn（VI，V，IV）=O）可能提供了大大增强的多氧化剂条件。所提出的“POA-金属”系统可以增强（i）烃的C-H键活化，和（ii）水的净化。该项目结合了互补的实验室实验，动力学建模和计算化学计算，以阐明实现金属催化循环以及有机氧化高效率的机理细节。该奖项反映了NSF的法定使命，并通过使用基金会的知识价值和更广泛的影响审查标准进行评估，被认为值得支持。

With support from the Environmental Chemical Sciences Program of the NSF Division of Chemistry, Professors Ching-Hua Huang of Georgia Institute of Technology and Virender Sharma of Texas A&M University will study multi-oxidant systems that involve peroxy acids (POA) and metals, for applications in water treatment. POA, ferrate(VI) and permanganate(VII) are well-recognized oxidants, but each shows some limitations individually. The project will explore the combination of POA with high valent metal (HVM) or low valent metal (LVM) ions in a multi-oxidant system that can degrade contaminants in water treatment and activate chemical bonds in organic synthesis. This project aims to elucidate the fundamental reaction kinetics and mechanisms to maximize the application potential. Additionally, this project will enhance education and broaden participation of underrepresented groups. Example activities include teaching and recruiting minority students to participate in research though partnerships with nine minority institutions in Georgia and Texas and teaching K-12 STEM (science, technology, engineering and mathematics) teachers. The interaction of POA with either high-valent metal (HVM) (e.g., ferrate(VI) and permanganate(VII)) or low-valent metal (LVM) (e.g., Fe(II) and Mn(II)) species can significantly enhance the degradation of water contaminants. The generation of POA-based radicals and intermediate high-valent metal oxo species (e.g., Fe(V, IV)=O, Mn(VI, V, IV)=O) likely provides the much enhanced multi-oxidants conditions. The proposed “POA-Metal” system can enhance (i) the C-H bond activation of hydrocarbons, and (ii) decontamination of water. This project combines complementary laboratory experiments, kinetic modeling, and computational chemistry calculations in an effort to elucidate mechanistic details to achieve catalytic cycling of the metal as well as high efficiency in the organic oxidation. The new insights into the combined oxidants have the possibility of generating robust catalytic oxidative systems for use in both synthetic chemistry and water treatment.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.