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

RUI：利用分子氧和可见光生产高反应性金属氧物种，用于选择性氧化催化

• 批准号: 1764315
• 负责人: Rui Zhang
• 金额: $ 25.01万
• 依托单位: Western Kentucky University Research Foundation
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2018
• 资助国家: 美国
• 起止时间: 2018-09-01 至 2022-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1764315&HistoricalAwards=false
• 关键词: RUI; Production; Highly; Reactive; Metal

The reaction of organic compounds with the oxygen in air with a catalyst is one of most important processes conducted daily on a large scale for the production of valuable chemicals, remediation of pollutants, and the production of energy. In this project, Dr. Rui Zhang and his students at Western Kentucky University (WKU) are designing efficient catalysts that can use sunlight to activate the atmospheric oxygen and transfer it to inexpensive materials for production of high-value commodity chemicals. The use of solar energy and atmospheric oxygen rather than a chemical reagent in oxidation of bulk chemicals is more sustainable, generates less chemical waste, and potentially reduces economic costs. This research impacts the fundamental science and technology of green chemistry. The project is providing cutting-edge research experiences for the participating undergraduate students in science, technology, engineering and mathematics (STEM) disciplines and thereby training future STEM professionals. High school students from the Gatton Academy, the residential Math and Science Academy located on WKU's campus, are also spending time in the laboratory and learning about catalysis research.With this award through the Chemical Catalysis Program, Dr. Rui Zhang and his students at Western Kentucky University are developing sustainable, "green" and selective oxidation catalysis via high-valent transition metal-oxo species, using molecular oxygen and visible light (sunlight). Prior studies in this area have demonstrated the unique reactivity of a series of oxo bisporphyrins and oxo corroles as useful photocatalysts. They can be used for oxidations in which high-valent transition metal-oxo species are produced through a disproportionation reaction. The salen-based catalysts are accepted as one of the most successful and widely applicable catalytic systems. However, mechanistic studies on these salen systems have so far been hampered by the fact that the catalytically active species appear only as fleeting putative intermediates. Now Prof. Zhang is exploring new ways to produce and elucidate the salen-metal-oxo oxidizing species, a challenging task. A variety of metal-salen complexes that contain photo-absorbing groups are being synthesized and investigated in an effort to capture a broad spectrum of light. The findings from this work are extending the scope of metal-oxo chemistry and exploring reactivity patterns of salen-metal-oxo complexes. More importantly, the synthesis and study of a series of oxo bis-metal-salens with attached light-harvesting units are leading to the new generation of photocatalysts for important aerobic oxidations. In addition, this award enables Dr. Rui Zhang to maintain a strong undergraduate research program, actively engage STEM students in all stages of the research projects. This effectively prepares them as future STEM professionals.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

有机化合物与空气中的氧与催化剂的反应是每天大规模进行的最重要的过程之一，用于生产有价值的化学物质，污染物的修复和能源的产生。在这个项目中，瑞张博士和他的学生在西肯塔基大学（WKU）正在设计有效的催化剂，这些催化剂可以使用阳光来激活大气氧，并将其转移到廉价的材料中，以生产高价值商品化学品。在散装化学物质的氧化中使用太阳能和大气氧，而不是化学试剂更可持续，产生更少的化学废物，并可能降低经济成本。这项研究影响了绿色化学的基本科学和技术。该项目正在为参与科学，技术，工程和数学（STEM）学科的参与本科生提供尖端的研究经验，从而培训未来的STEM专业人员。来自加顿学院的高中生，位于WKU校园位于WKU校园的住宅数学和科学学院，也在实验室里花费时间并学习催化研究。通过化学催化计划，该奖项通过化学催化计划，Rui Zhang博士和他的西肯塔基大学的学生通过可持续发展的可持续性和选择性的氧化式旋转，“绿色和选择性的氧化型”，“绿色”，“绿色”，“绿色”和“选择性氧化型”，“绿色”和“绿色”奖。 （阳光）。在该领域的先前研究表明，一系列氧甲甲蛋白和Oxo Crololes作为有用的光催化剂的独特反应性。它们可用于氧化，其中高价值过渡金属氧化物种是通过不成比例的反应产生的。基于沙伦的催化剂被接受为最成功，最广泛适用的催化系统之一。然而，到目前为止，对这些沙伦系统的机理研究受到了催化活性物种仅作为短暂推定的中间体的事实的阻碍。现在，张教授正在探索新的方法来生产和阐明Salen-Metal-Oxo氧化物种，这是一项艰巨的任务。正在合成和研究包含吸收光吸收基团的各种金属盐络合物，以捕捉广泛的光谱。这项工作的发现扩大了金属氧化学的范围，并探索了沙伦 - 金氧络合物的反应性模式。更重要的是，对一系列具有附着的轻度收获单元的Oxo Bis-Metal-salens的合成和研究导致新一代的光催化剂用于重要的有氧氧化。此外，该奖项使Rui Zhang博士能够维持强大的本科研究计划，并在研究项目的各个阶段积极吸引STEM学生。这有效地为未来的STEM专业人员做好了准备。该奖项反映了NSF的法定任务，并被认为是值得通过基金会的知识分子优点和更广泛影响评论标准的评估来支持的。

项目成果

Synthesis of a light-harvesting ruthenium porphyrin complex substituted with BODIPY units. Implications for visible light-promoted catalytic oxidations

• DOI: 10.1039/d1nj00189b
• 发表时间: 2021-03
• 期刊: New Journal of Chemistry
• 影响因子: 3.3
• 作者: J. Malone;Seth Klaine;C. Alcantar;Fox Bratcher;Rui Zhang

Formation and kinetic studies of manganese(IV)-oxo porphyrins: Oxygen atom transfer mechanism of sulfide oxidations

• DOI: 10.1016/j.jinorgbio.2019.110986
• 发表时间: 2020-03-01
• 期刊: JOURNAL OF INORGANIC BIOCHEMISTRY
• 影响因子: 3.9
• 作者: Klaine, Seth;Bratcher, Fox;Zhang, Rui
• 通讯作者: Zhang, Rui

Visible light generation of chromium(V)-oxo salen complexes and mechanistic insights into catalytic sulfide oxidation

• DOI: 10.1016/j.ica.2020.119681
• 发表时间: 2020-09
• 期刊: Inorganica Chimica Acta
• 影响因子: 2.8
• 作者: Seth Klaine;Ngo Fung Lee;Angeline Dames;Rui Zhang

Synthetic and mechanistic investigations on manganese corrole-catalyzed oxidation of sulfides with iodobenzene diacetate

• DOI: 10.1016/j.ica.2018.11.048
• 发表时间: 2019-03
• 期刊: Inorganica Chimica Acta
• 影响因子: 2.8
• 作者: Davis Ranburger;Ben E. Willis;Benjamin Kash;H. Jeddi;C. Alcantar;Rui Zhang