ELECTROCATALYTIC REDUCTION OF HALOGENATED BIPHENYLS

这个项目的长期目标是开发新的 电催化方法实现清洁、永久有效的销毁 减少多氯联苯等卤化有机污染物的排放，并提供新的见解 这些化合物的毒性和环境相互作用 建立了它们电子转移反应的基本细节。 技术将适用于相关有毒卤代化学品 我们的环境，如氯化二苯并二恶英、二苯并呋喃、乙烯 二溴(EDB)和氯化农药。下一步的具体目标 五年包括优化催化系统以更快地实现 在降低成本和能源投入的同时，提高脱卤率。电极 将被涂上预浓缩的催化表面活性剂薄膜 反应物。由于在自然环境中发现了水中的污染物， 散装反应介质将使用有组织的水基流体，称为 微乳液。表面活性剂/催化剂系统将专门定制 用于完全分解商业多氯联苯和多溴联苯混合物以及其他 结合在土壤、沉积物和工业油中的有机卤化物。新的 低表面活性剂含量的导电水/油/表面活性剂微乳液 将被评估为低成本的反应介质，避免了替代毒性 溶剂。我们将使用金属大环配合物来催化 能量投入极低、催化效率高的分解反应 效率。我们还将研究表面活性剂中蛋白质的催化作用。 电影。除了提供低能量的脱卤素，氧化还原蛋白- 表面活性剂薄膜可能提供对污染物有毒相互作用的洞察 微生物和哺乳动物。 阴离子自由基是生物、化学和生物合成的关键中间体。 多氯联苯的光化学脱氯。这些活性物种可能是 对基因损伤负有部分责任。寿命和标准势 对于多氯联苯，阴离子自由基将在微乳液中进行测量。结果应该是 促进对卤代联苯的环境相互作用的深入了解 在模拟自由基的可能环境的有组织的介质中 在生命系统中。这些关于有机卤化物的基本数据将是有用的 将结构与毒性和微生物反应性联系起来。 预计这项研究将对解决方案做出重大贡献 关于我们环境污染的公共卫生问题 有机卤化物化学品，这反过来将改善未来的健康 我们的公民。它承诺产生新的方法来永久地 有效清理沉积物、土壤和 工业用油。我们的基本成果将有助于旨在 揭示三氯甲烷的毒性和环境相互作用机制 无处不在的持久性有机卤化物污染物。

The broad long-term objectives of this project are to develop new electrocatalytic approaches for clean, permanently effective destruction of halogenated organic pollutants such as PCBs and to provide new insights into toxic and environmental interactions of these compounds by establishing fundamental details of their electron-transfer reactions. Techniques will be applicable to related toxic halogenated chemicals in our environment like chlorinated dibenzodioxins, dibenzofurans, ethylene dibromide (EDB), and chlorinated pesticides. Specific aims for the next five years include optimizing catalytic systems to attain faster dehalogenation rates while decreasing cost and energy input. Electrodes will be coated with catalytic surfactant films which preconcentrate reactants. Since pollutants are found with water in natural environments, bulk reaction media will employ organized water-based fluids called microemulsions. Surfactant/catalyst systems will be tailored specifically for complete decomposition of commercial PCB and PBB mixtures and other organohalides bound to soils and sediments and in industrial oils. New conductive water/oil/surfactant microemulsions with low surfactant content will be evaluated as low cost reaction media which avoid alternative toxic solvents. We will employ metal macrocyclic complexes to catalyze decomposition reactions with very low energy input and high catalytic efficiency. We will also investigate catalysis by proteins in surfactant films. In addition to providing low energy dehalogenations, redox protein- surfactant films may provide insight into toxic interactions of pollutants with microorganisms and mammals. Anion radicals are key intermediates in biological, chemical, and photochemical dechlorinations of PCBs. These reactive species may be partly responsible for genetic damage. Lifetimes and standard potentials for PCB anion radicals will be measured in microemulsions. Results should lead to improved insight into environmental interactions of halobiphenyls in an organized medium which mimics possible environments of the radicals in living systems. These fundamental data on organohalides will be useful in correlating structure with toxic and microbiological reactivities. This research is expected to yield significant contributions to a solution of the public health problem of contamination of our environment with organohalide chemicals, which in turn will improve the future health of our citizens. It promises to generate new approaches to permanently effective cleanup of contaminated materials such as sediments, soils, and industrial oils. Our fundamental results will aid in research aimed at uncovering mechanisms of toxicity and environmental interactions of ubiquitous and persistent organohalide pollutants.