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气在催化剂下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品，污染物的修复和能源的生产。在这个项目中，Rui Zhang博士和他在西肯塔基州大学（WKU）的学生正在设计高效的催化剂，可以利用阳光激活大气中的氧气，并将其转化为廉价的材料，用于生产高价值的商品化学品。在大宗化学品的氧化中使用太阳能和大气氧气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。这一研究对绿色化学的基础科学和技术产生了重要影响。该项目为参与的本科生提供科学，技术，工程和数学（STEM）学科的前沿研究经验，从而培养未来的STEM专业人员。来自加顿学院（位于西肯塔基大学校园内的住宿数学和科学学院）的高中生也在实验室里学习催化研究。通过化学催化项目获得这个奖项，张锐博士和他在西肯塔基州大学的学生正在开发可持续的、“绿色”的和通过高价过渡金属氧物种选择性氧化催化，利用分子氧和可见光（太阳光）。在这一领域的先前研究已经证明了一系列的氧代双卟啉和氧代可罗莱作为有用的光催化剂的独特的反应性。它们可用于氧化反应，其中高价过渡金属-氧代物质通过反硝化反应产生。Salen基催化剂被公认为是最成功和应用最广泛的催化体系之一。然而，迄今为止，这些萨伦体系的机理研究受到阻碍的事实，即催化活性物种似乎只是作为短暂的假定中间体。现在，张教授正在探索新的方法来生产和阐明Salen金属氧氧化物种，这是一项具有挑战性的任务。各种含有光吸收基团的金属-salen络合物正在被合成和研究，以努力捕获宽光谱的光。这些发现拓展了金属-氧代化学的研究范围，并探索了Salen-金属-氧代配合物的反应模式。更重要的是，一系列带有捕光单元的含氧双金属salens的合成和研究正在导致新一代的光催化剂用于重要的好氧氧化。此外，该奖项使张锐博士能够保持强大的本科研究计划，积极吸引STEM学生参与研究项目的各个阶段。该奖项反映了NSF的法定使命，并通过使用基金会的知识价值和更广泛的影响审查标准进行评估，被认为值得支持。

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

Kinetics of chromium(V)-oxo and chromium(IV)-oxo porphyrins: Reactivity and mechanism for sulfoxidation reactions.

• DOI: 10.2139/ssrn.4163383
• 发表时间: 2022-09
• 期刊: Journal of inorganic biochemistry
• 影响因子: 3.9
• 作者: Tristan Skipworth;Mardan Khashimov;Iyanu Ojo;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