RUI: Production of Highly Reactive Metal-Oxo Species with Molecular Oxygen and Visible Light for the Selective Oxidative Catalysis

在这个由化学学部化学催化项目资助的项目中，西肯塔基大学的张瑞教授正在设计高效的光催化剂（在光输入的情况下起作用的催化剂），它可以利用阳光激活氧气并将其转移到其他化学物质中，也称为氧化。在散装化学品的氧化过程中，使用阳光和大气中的氧气而不是化学试剂将更可持续，产生更少的化学废物，并可能降低与该过程相关的经济成本。该研究将对绿色化学的基础科学技术产生重大影响。该项目为参与的STEM本科生提供尖端的研究经验，从而培养未来的STEM专业人员。来自加顿学院的高中生也花时间在实验室学习催化研究。Zhang正在研究如何在催化循环中通过muo -oxo金属（IV）二聚体的光歧化产生高活性的金属(V)-oxo物种。在这个研究实验室的初步研究已经证明了钌（IV） mu-氧双卟啉和铁（IV） mu-氧共聚物的独特反应活性，其中高价过渡金属氧中间体通过歧化获得。现在，张教授正在研究如何通过光歧化反应产生更活跃的锰(V)-氧，并开发更稳定的金属或角色配合物催化的高效氧化。目前正在开发将光敏剂与催化剂连接的合成途径，以提高催化剂的光收集效率。

In this project funded by the Chemical Catalysis Program of the Chemistry Division, Professor Rui Zhang at the Western Kentucky University is designing efficient photocatalysts (catalysts that function with the input of light) that can utilize sunlight to activate oxygen and transfer it to other chemicals, also termed oxidation. The use of sunlight and atmospheric oxygen rather than a chemical reagent in the oxidation processes of bulk chemicals would be more sustainable, generate less chemical waste, and potentially reduce economic costs associated with the process. The research may impact the fundamental science and technology of green chemistry. The project is providing cutting-edge research experiences for the participating undergraduate STEM students and thereby training future STEM professionals. High school students from Gatton Academy are also spending time in the laboratory and learning about catalysis research.Dr. Zhang is studying ways to produce highly reactive metal(V)-oxo species in a catalytic cycle through photo-disproportionation of mu-oxo metal(IV) dimers. Initial studies in this research laboratory have demonstrated unique reactivity of ruthenium(IV) mu-oxo bisporphyrins and iron(IV) mu-oxo corroles in which high valent transition-metal oxo intermediates are accessed through the disproportionation. Now, Prof. Zhang is studying ways to produce the more reactive manganese(V)-oxo species via photo-disproportionation reactions and to develop efficient oxidations catalyzed by more stable metallocorrole complexes. Synthetic pathways are being developed to link a photosensitizer to the catalyst and to improve the light harvesting efficiency of the catalyst.