ELECTROCATALYTIC REDUCTION OF HALOGENATED BIPHENYLS

该项目的长期目标是开发新的 采用电催化方法进行清洁、永久有效的销毁 卤化有机污染物，如多氯联苯，并提供新的见解 这些化合物的毒性和环境相互作用， 建立电子转移反应的基本细节。 技术将适用于相关的有毒卤化化学品， 我们的环境，如氯化二苯并二恶英，二苯并呋喃，乙烯 二溴化物（EDB）和氯化农药。未来的具体目标 五年包括优化催化系统， 脱卤速率，同时降低成本和能量输入。电极 将被涂上催化表面活性剂膜， 反应物由于污染物在自然环境中与水一起发现， 本体反应介质将采用有序的水基流体， 微乳液表面活性剂/催化剂系统将专门定制 用于完全分解商用多氯联苯和多溴联苯混合物及其他 土壤和沉积物以及工业油中的有机卤化物。新 具有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， 溶剂.我们将采用金属大环配合物催化 具有非常低的能量输入和高催化活性的分解反应 效率我们还将研究表面活性剂中蛋白质的催化作用 薄膜.除了提供低能量脱卤，氧化还原蛋白- 表面活性剂膜可提供对污染物的毒性相互作用的了解 微生物和哺乳动物。 阴离子自由基是生物、化学和生物技术中的关键中间体。 多氯联苯的光化学脱氯。这些活性物质可以是 部分原因是遗传损伤。寿命和标准电位 对于PCB阴离子自由基，将在微乳液中测量。结果应 从而更好地了解卤代联苯与环境之间相互作用 在模拟自由基可能环境的有组织介质中， 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。 这项研究预计将产生重大贡献的解决方案 我们的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 我们的公民它有望产生新的方法， 有效清除污染物质，如沉积物，土壤， 工业油。我们的基本成果将有助于研究， 揭示毒性和环境相互作用的机制， 普遍存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.