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

在化学系化学催化计划的支持下，西肯塔基大学(WKU)的张瑞教授将研究有机化合物与大气中的氧气在催化剂作用下的反应，这一过程被称为催化有氧氧化。这一过程每天被广泛地大规模用于生产有价值的化学品、污染物的环境修复以及能源生产。张锐博士和他在西卡罗来纳大学的学生们正在努力开发受生物启发的光催化剂，这种催化剂可以利用阳光来激活并将大气中的氧气结合到廉价的材料中，以生产高价值的商品化学品。使用丰富的太阳能和大气氧气而不是化学试剂来氧化大宗化学品产生的化学废物更少，在化学上更可持续，并有可能降低与该过程相关的经济成本。这项研究将对绿色化学的基础科学技术产生影响。此外，该项目将为参与的本科生提供尖端研究经验，包括科学、技术、工程和数学(STEM)学科的贫困学生和女性，从而培养未来的STEM专业人员。来自全国著名的Gatton Academy、位于西九龙大学校园的住宅区数学与科学学院的高中生也将在实验室进行研究，了解催化研究。在这项研究中，张睿教授和他的团队将研究金属酞菁配合物(MPC)作为可持续和“绿色”的氧化催化剂，因为它们易于获得，并具有出色的氧化还原和光学性能。这项研究将集中在MPC催化中涉及的机理研究和金属氧氧化物种的生成，并将利用所获得的新知识来开发可行和实用的清洁氧化催化方法。尽管MPC是非常有吸引力的催化剂，在许多氧化过程中都有广泛的应用，但MPC催化氧化的机理和MPC基金属氧代活性中间体的鉴定还不够成熟。不同大环体系中的高价过渡金属氧氧化剂可以通过光化学反应生成，并通过歧化反应用于氧化。在这个项目中，张博士和他在西科大的学生们旨在探索新的方法来探索活性氧化物种的性质，并阐明在MPC介导的催化中存在的机制。重要的是，我们将合成各种含有光吸收单元的新型MPC催化剂，并将其用于光催化有氧氧化。这项研究有望促进金属-氧化学和光催化方面的知识，并对催化剂中太阳能的转化产生长期影响。该奖项反映了NSF的法定使命，并通过使用基金会的智力优势和更广泛的影响审查标准进行评估，被认为值得支持。

With the support of the Chemical Catalysis Program in the Division of Chemistry, Professor Rui Zhang of Western Kentucky University (WKU) will study the reaction of organic compounds with oxygen from the atmosphere using catalysts, in a process called catalytic aerobic oxidation. This process is widely used daily on a large scale for the production of valuable chemicals, the environmental remediation of pollutants, and in the production of energy. Dr. Rui Zhang and his students at WKU are working to develop bio-inspired photocatalysts that can utilize sunlight to activate and incorporate atmospheric oxygen into inexpensive materials for producing high-value commodity chemicals. The use of abundant solar energy and atmospheric oxygen rather than a chemical reagent in the oxidation of bulk chemicals generates less chemical waste, is more chemically sustainable, and potentially reduces the economic costs associated with the process. The research will impact the fundamental science and technology of green chemistry. In addition, this project will provide cutting-edge research experiences for the participating undergraduate students, including underserved students and women in science, technology, engineering, and mathematics (STEM) disciplines, thereby training future STEM professionals. High school students from the nationally renowned Gatton Academy, the residential Math and Science Academy located on WKU’s campus, will also perform research in the laboratory and learn about catalysis research.In this research, Professor Rui Zhang and his team will study metal phthalocyanine complexes (MPc’s) as sustainable and “green” oxidation catalysts in view of their easy accessibility and outstanding redox and optical properties. This research will focus on mechanistic studies and the generation of metal-oxo oxidizing species involved in MPc-based catalysis, and will use the new knowledge obtained to develop viable and practical catalytic methods for clean oxidations. Although MPc’s are very attractive and are widely applicable catalysts in many oxidation processes, mechanistic aspects of MPc-catalyzed oxidations and identification of the MPc-based metal-oxo reactive intermediates are still underdeveloped. High-valent transition metal-oxo oxidants in different macrocyclic systems can be generated photochemically and used for oxidations through disproportionation reactions. In this project, Dr. Zhang and his students at WKU aim to explore new ways to probe the nature of active oxidizing species and elucidate mechanisms extant in MPc-mediated catalysis. Importantly, a variety of new MPc-based catalysts that contain photoabsorbed units will be synthesized and investigated for photocatalytic aerobic oxidations. This research is expected to advance knowledge in metal-oxo chemistry and photocatalysis and to have long term implications for the conversion of solar energy in catalysis.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.