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

在这个由化学系化学催化计划资助的项目中，西肯塔基大学的张睿教授正在设计高效的光催化剂(利用光的输入作用的催化剂)，它可以利用阳光激活氧气并将其转移到其他化学物质，也称为氧化。在大宗化学品的氧化过程中使用阳光和大气氧气而不是化学试剂将更可持续，产生更少的化学废物，并有可能降低与该过程相关的经济成本。这项研究可能会对绿色化学的基础科学和技术产生影响。该项目为参与的STEM本科生提供尖端研究经验，从而培养未来的STEM专业人员。加顿学院的高中生也在实验室里学习催化研究。张正在研究通过钼氧金属(IV)二聚体的光歧化在催化循环中产生高活性金属(V)-氧物种的方法。该研究实验室的初步研究表明，Ru(IV)Mu-oxo双卟啉和Fe(IV)Mu-Ox腐蚀剂具有独特的反应活性，其中高价过渡金属氧基中间体通过歧化反应获得。现在，张教授正在研究如何通过光歧化反应生成活性更高的锰(V)-氧物种，并开发更稳定的金属配合物催化有效的氧化反应。正在开发合成途径，将光敏剂连接到催化剂上，并提高催化剂的捕光效率。

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.