Electrochemical Oxidation in Room Temperature Ionic Liquids

这个项目的目的是证明环境上可接受的方法完全氧化氯化溶剂的环境修复。在非质子室温离子液体中，利用合适的阴极生成超氧离子。除了证明氯化污染物的完全氧化外，使用相同的超氧化物化学的部分电化学氧化将为合成羧酸的功能衍生物有机分子提供一条途径。该PI将在新型离子液体溶剂中通过电化学生成超氧离子对废物进行低温氧化。废溶剂的低温氧化将为高温废物焚化炉提供一种急需的替代方案，高温废物焚化炉的使用因法规要求和选址合适而变得非常复杂。这种超氧化物化学先前已在挥发性和环境可疑的非质子溶剂（如二甲基甲酰胺和乙腈）中得到证实。然而，离子液体是非挥发性和不易燃的，应该尽量减少二次溶剂浪费和产品与溶剂分离的问题。假设超氧化物的基本电化学反应是成功的，进一步提出通过电化学激活二氧化碳（CO2）和氧气，然后适当的底物羧化进行有机合成。要合成的分子类别是氨基酰胺，它是生产消费品（如药品和农药）的有价值的中间体。目前的商业工艺可能需要有机溶剂、昂贵的催化剂，甚至光气来合成这些中间体。因此，有强烈的动机采用更好的、可持续的方法来制造这些中间体。该项目支持开发一种基于超氧化物化学的清洁环保技术，用于废物修复和化学品制造。该项目将涉及一名研究生、一名博士后和本科生，通过南卡罗来纳大学化学工程系现有的NSF REU项目。

The objective of this project is to demonstrate environmentally-acceptable methods for complete oxidation of chlorinated solvents for environmental remediation. The active oxygenation species will be superoxide ion, which will be generated in an aprotic room temperature ionic liquid using a suitable cathode. In addition to demonstrating complete oxidation of chlorinated pollutants, partial electrochemical oxidation using the same superoxide chemistry will provide a route for synthesis of organic molecules that are functional derivatives of carboxylic acids.The PI will conduct low-temperature oxidation of wastes via electrochemical generation of superoxide ion in novel ionic liquid solvents. Low-temperature oxidation of waste solvents will provide a much-needed alternative to high temperature waste incinerators, whose use is greatly complicated by regulatory requirements and locating suitable sites. Such superoxide chemistry has previously been demonstrated in volatile and environmentally-suspect aprotic solvents such as dimethyl formamide and acetonitrile. However, ionic liquids are non-volatile and non-flammable, and should minimize the problems of secondary solvent waste and separation of products from solvent. Assuming the basic electrochemistry of superoxide is successful, it is further proposed to conduct organic synthesis by electrochemical activation of carbon dioxide (CO2) and oxygen, followed by carboxylation of appropriate substrates. The classes of molecules to be synthesized are carbamides, which are valuable intermediates in the production of consumer products such as pharmaceuticals and agrichemicals. Present commercial processes may require organic solvents, expensive catalysts, or even phosgene in the synthesis of these intermediates. There is thus a strong motivation for better, sustainable approaches to manufacture of these intermediates.This project supports the development of a clean and environmentally friendly technology for both waste remediation and chemical manufacturing, based on superoxide chemistry. The project will involve a graduate student, a post-doctoral student, and undergraduate students through an existing NSF REU program in the Department of Chemical Engineering at the University of South Carolina.