CRAEMS: Environmental Redox-Mediated Dehalogenation Chemistry

约翰霍普金斯大学环境分子科学合作研究活动奖由化学学部特别项目办公室支持。该奖项支持Gerald Meyer、Howard Fairbrother、David Goldberg、Kenneth Karlin和A. Lynn Roberts在脱卤化学方面的研究，这些研究结合了他们在合成、均相和异相催化、仿生和生物无机化学、电化学、表面科学和环境化学方面的专业知识。这个多学科项目的具体目标是：1)新的还原和氧化脱卤化学的发展和其基本机制的阐明；2)这些新发现在有机卤化物污染物的感知、修复和环境命运测定中的应用；3)提供一个教学平台，告知和教育下一代环境化学家。基础研究将着重于铜(I)和金属卟啉配合物对有机卤化物的氧化和还原裂解。化学计量和电催化过程都将被研究。光触发和电化学脱卤也将被检查。探索利用双金属还原剂和金属硫化物矿物进行脱卤。最后，电子束诱导的氯碳还原解理将在水和冰介质中进行研究。合作伙伴包括两个国家实验室（橡树岭国家实验室和太平洋西北国家实验室）和两个行业（KDF流体处理公司和环境技术集团公司）。为了在分子水平上发展对环境原理和过程的理解，将开发和教授一门新的研究生课程。将实施一项涉及来自附近大学（霍华德大学和摩根州立大学）代表性不足的本科生研究人员的外展计划。美国前25种有机污染物中有17种是有机卤化物。挥发性有机卤化物也会消耗臭氧并改变全球气候。这项跨学科的工作旨在从分子水平上理解氧化还原介导的脱卤，由此可以开发“更环保”的化学工艺，并消除由有机卤化物引起的污染问题。这个多学科项目的教育方面，与政府实验室和行业合作，旨在提高学生对现实世界环境问题的认识，并提供实践经验。

This Collaborative Research Activities in Environmental Molecular Science (CRAEMS) Award to Johns Hopkins University is supported by the Special Projects Office of the Chemistry Division. The award supports studies by Gerald Meyer, Howard Fairbrother, David Goldberg, Kenneth Karlin and A. Lynn Roberts of dehalogenation chemistry by combining their expertise in synthesis, homogeneous and heterogeneous catalysis, biomimetic and bioinorganic chemistry, electrochemistry, surface science, and environmental chemistry. Specific goals of this multidisciplinary program are: 1) the development of new reductive and oxidative dehalogenation chemistries and the elucidation of their fundamental mechanisms; 2) application of these new findings to the sensing, remediation, and determination of the environmental fate of organohalide pollutants; and 3) provide a pedagogical platform that informs and educates the next generation of environmental chemists. The fundamental studies will emphasize oxidative and reductive cleavage of organohalides by copper (I) and metalloporphyrin complexes. Both stoichiometric and electrocatalytic processes will be studied. Photo-triggered and electrochemical dehalogenation will also be examined. Dehalogenation by bimetallic reductants and metal sulfide minerals will be explored. Finally, electron-beam-induced chlorocarbon reductive cleavage will be examined in water and ice media. Collaborations include those with two National Laboratories (Oak Ridge National Laboratory and Pacific Northwest National Laboratory) and with two industries (KDF Fluid Treatment Inc., and Environmental Technologies Group Inc.). To develop an understanding of environmental principles and processes at the molecular level, a new graduate course will be developed and taught. An outreach program involving underrepresented undergraduate researchers from nearby universities (Howard University and Morgan State University) will be implemented.Seventeen of the top twenty-five organic pollutants in the U.S. are organohalides. Volatile organohalides also deplete ozone and change global climate. This interdisciplinary work aims at a molecular-level understanding of redox-mediated dehalogenation, from which "greener" chemical processes can be developed and pollution problems due to organic halides can be obviated. The educational aspects of this multidisciplinary program, in collaboration with government laboratories and industries, is designed to increase the awareness of students concerning real-world environmental problems and to provide hands-on experience.