Collaborative Research: Design and Study of Chalcogen-Containing Cationic Dyes for Photocatalysis

合作研究：光催化含硫阳离子染料的设计与研究

• 批准号: 1800599
• 负责人: Theresa McCormick
• 金额: $ 29.17万
• 依托单位: Portland State University
• 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: 2018-07-01 至 2022-06-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1800599&HistoricalAwards=false
• 关键词: Collaborative; Research; Design; Study; Chalcogen

The development of methods to transform molecules into useful materials and products is a key challenge facing chemists. One common transformation is an oxidation reaction, where oxygen is added to or electrons are removed from a molecule. Oxidation reactions often rely on toxic reagents that produce a large amount of waste. The use of molecular oxygen could reduce both the cost of these reactions and the amount of waste produced. Molecular oxygen is also abundant in air. Scientists generally do not know how to use atmospheric oxygen to transform molecules into desired products. In this project, Dr. McCormick of Portland State University and Drs. Detty and Cook of the University at Buffalo are investigating dyes that can use energy from light to make desirable molecular transformations with atmospheric oxygen. By understanding how changing the structure of a dye influences its reactivity, it may be possible to control and target these oxidation reactions. Drs. McCormick, Detty, and Cook are dedicated to increasing education in areas of sustainability via the implementation of new courses. They provide research internships to students to increase their awareness of the impact of development on the environment and their role as scientists in creating sustainable solutions. The curriculum revisions may increase student engagement in issues of sustainability and photochemistry. The modules are disseminated to allow schools across the country to adopt the curriculum, which focuses on on principles of green chemistry, environmental protection, and renewable energy. A more engaged and informed science workforce may be better able to solve current and future problems of sustainability.Drs. McCormick, Detty, and Cook are supported by the Chemical Catalysis Program of the Chemistry Division to investigate chalcogen-containing dyes as photosensitizers for photocatalytic redox reactions. The use of photo-induced redox catalysis for synthetic transformations is of interest due to its potential for the green production of small molecules at both laboratory and industrial scale. The interchange of the chalcogen atoms (O, S, or Se to Te) in the xanthylium or pyrylium core of the dyes allows control of redox behavior in the dyes, as well as wavelengths of absorption, fluorescence yields and lifetimes, and triplet yields and lifetimes. The chalcogen-containing dyes function as photo-oxidants in that the excited state can accept an electron to give a one-electron oxidation of a substrate. The excited state can also intersystem-cross from singlet to triplet and then interact with ground-state oxygen to generate singlet-oxygen, which can function as a potent oxidant. This research may result in a decreased reliance on fossil fuels by providing a route to hydrogen peroxide production, decreasing carbon emissions.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.

将分子转化为有用材料和产品的方法的发展是化学家面临的关键挑战。一种常见的转化是氧化反应，其中将氧气添加到分子中或从分子中除去电子。氧化反应通常依赖于产生大量废物的有毒试剂。 分子氧的使用可以降低这些反应的成本和产生的废物量。空气中的分子氧也很丰富。 科学家通常不知道如何使用大气氧将分子转化为所需产品。在这个项目中，波特兰州立大学的麦考密克博士和博士。布法罗大学的Detty and Cook正在研究染料，这些染料可以利用光能从光中使用大气氧进行理想的分子转化。通过了解改变染料的结构如何影响其反应性，可以控制和靶向这些氧化反应。博士。 McCormick，Detty和Cook致力于通过实施新课程来增加可持续性领域的教育。他们为学生提供研究实习，以提高他们对发展对环境的影响及其在创建可持续解决方案中的作用的认识。 课程修订可能会增加学生参与可持续性和光化学问题。这些模块被散布以允许全国各地的学校采用该课程，该课程的重点是绿色化学，环境保护和可再生能源的原则。更具参与和知情的科学劳动力可能能够更好地解决可持续性的当前和未来问题。 McCormick，Detty和Cook得到了化学划分的化学催化程序的支持，以研究含有沙尔氏蛋白原的染料作为光催化氧化还原反应的光敏剂。由于其在实验室和工业规模上绿色的小分子的潜力，因此使用光诱导的氧化还原催化进行合成转化引起了人们的关注。染料的Xanthylium或pyrylium核心的chalcogen原子（O，S或SE至TE）的互换允许控制染料中的氧化还原行为，以及吸收，荧光产量和寿命的波长，以及三重率的产量和寿命。含chalcogen的染料充当光氧化剂，因为激发态可以接受电子以对底物的单电子氧化。激发态还可以从单线到三重螺旋体之间的交叉交叉，然后与地面氧相互作用，产生单重氧，可以用作有效的氧化剂。 这项研究可能通过提供过氧化氢的途径，减少碳排放量来减少对化石燃料的依赖。该奖项反映了NSF的法定任务，并且认为值得通过基金会的智力优点评估来获得支持，并具有更广泛的影响。

项目成果

Singlet oxygen quantum yields determined by oxygen consumption

• DOI: 10.1016/j.jphotochem.2019.04.029
• 发表时间: 2019-06-01
• 期刊: JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY
• 影响因子: 4.3
• 作者: Lutkus, Luke, V;Rickenbach, Sam S.;McCormick, Theresa M.
• 通讯作者: McCormick, Theresa M.

Empirical DFT Model to Predict Triplet Quantum Yield Through Singlet Oxygen Yields

通过单线态氧产率预测三线态量子产率的经验 DFT 模型

• DOI: 10.1002/cptc.202100205
• 发表时间: 2022
• 期刊: ChemPhotoChem
• 影响因子: 3.7
• 作者: Steinkamp, Bret A.;Lutkus, Luke V.;Lewis, Rob;McCormick, Theresa M.
• 通讯作者: McCormick, Theresa M.

Enrolling reactive oxygen species in photon-to-chemical energy conversion: fundamentals, technological advances, and applications

• DOI: 10.1080/23746149.2021.1950049
• 发表时间: 2021-01
• 期刊: Advances in Physics: X
• 作者: Irving D. Rettig;T. McCormick

Importance of Singlet Oxygen in Photocatalytic Reactions of 2-Aryl-1,2,3,4-tetrahydroisoquinolines Using Chalcogenorosamine Photocatalysts

• DOI: 10.1021/acs.organomet.9b00126
• 发表时间: 2019-06
• 期刊: Organometallics
• 影响因子: 2.8
• 作者: J. Clark;Jacqueline E. Hill;Irving D. Rettig;Joshua J. Beres;R. Ziniuk;Tymish Y. Ohulchanskyy;T. McCormick;M. Detty