LEAPS-MPS: CAS: Photoactivation of Metal-Oxo Bonds in Heterobinuclear Systems for Oxidative Catalysis

LEAPS-MPS：CAS：异双核系统中金属-氧键的光活化用于氧化催化

• 批准号: 2213341
• 负责人: Shabnam Hematian
• 金额: $ 25万
• 依托单位: University of North Carolina Greensboro
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2022
• 资助国家: 美国
• 起止时间: 2022-07-01 至 2024-06-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2213341&HistoricalAwards=false
• 关键词: LEAPS; MPS; CAS; Photoactivation; Metal

This award is funded in whole or in part under the American Rescue Plan Act of 2021 (Public Law 117-2). In this project, funded by the Mathematical and Physical Sciences Directorate and housed in the Chemistry Division, Professor Shabnam Hematian and her research team at the University of North Carolina at Greensboro will study catalytic processes to generate value-added chemicals from light, air, and simple compounds. As the demand for green chemistry and sustainable chemical design increases, the use of green energy sources such as light, rather than high energy chemical reagents, offers an energy-efficient means to transform cheap and unreactive raw materials into chemicals with higher molecular complexity and value. A photocatalyst must be used to capture the light and then act as an intermediary in the bond rearrangement reaction to form target products. Also, harnessing the oxidizing power of oxygen in the air (i.e., dioxygen) as a green terminal oxidant is of great interest. In this project, Professor Hematian and her team will attempt to develop new photocatalysts that can utilize dioxygen and absorb light to drive the air-oxidation of hydrocarbons, such as those found in petroleum products, to form alcohols, epoxides, and other valuable chemical products. The project will also provide research opportunities for local high school and community college students at earlier stages of their academic life as well as homeschooled high school students that typically have no access to these opportunities. A primary objective of the project to recruit students who are historically underrepresented in STEM, thus broadening participation and retention in the chemistry field.The project will focus on development of oxo-bridged heterobinuclear systems, in which the two different metal centers, such as iron and copper, are attached through an oxo ligand, via dioxygen chemistry. This class of oxo-bridged assemblies will then be investigated for the photoactivation of their metal-oxo bonds and overall catalytic activities. This effort and the modularity of the oxo-bridged assemblies will provide deeper insights into the reaction pathways to guide the design of next-generation aerobic photocatalysts in the pursuit of developing green oxidation processes. The project will also introduce research opportunities to homeschooled high school students and low-income first-generation community college students and will encourage high school students, particularly females and underrepresented minorities, to partake in the research experience as early as their Sophomore or Junior years.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.

该奖项全部或部分根据2021年美国救援计划法案（公法117-2）资助。 在这个项目中，由数学和物理科学理事会资助，并设在化学司，教授Shabnam Hematian和她的研究小组在北卡罗来纳州大学格林斯伯勒将研究催化过程，以产生增值的化学品从光，空气和简单的化合物。随着对绿色化学和可持续化学设计的需求的增加，使用绿色能源如光而不是高能化学试剂提供了一种将廉价且无反应性的原材料转化为具有更高分子复杂性和价值的化学品的节能手段。必须使用光催化剂来捕获光，然后在键重排反应中充当中间体以形成目标产物。此外，利用空气中氧气的氧化能力（即，分子氧）作为绿色终端氧化剂受到极大关注。在这个项目中，Hematian教授和她的团队将尝试开发新的光催化剂，可以利用分子氧和吸收光来驱动碳氢化合物的空气氧化，例如石油产品中发现的碳氢化合物，以形成醇，环氧化物和其他有价值的化学产品。该项目还将为当地高中和社区大学的学生提供研究机会，在他们的学术生活的早期阶段，以及在家上学的高中生，通常没有机会获得这些机会。该项目的主要目标是招收在STEM领域历史上代表性不足的学生，从而扩大化学领域的参与和保留。该项目将重点开发氧桥异双核系统，其中两个不同的金属中心，如铁和铜，通过氧配体连接，通过双氧化学。这类氧桥组装，然后将研究其金属氧键的光活化和整体催化活性。这一努力和模块化的氧桥组装将提供更深入的了解反应途径，以指导下一代有氧光催化剂的设计，追求发展绿色氧化过程。该项目还将为在家上学的高中生和低收入的第一代社区大学生提供研究机会，并鼓励高中生，特别是女性和代表性不足的少数民族，该奖项反映了NSF的法定使命，并被认为是值得通过使用基金会的智力价值和更广泛的影响审查标准。

项目成果

Oxygenation of copper(I) complexes containing fluorine tagged tripodal tetradentate chelates: significant ligand electronic effects

• DOI: 10.1080/00958972.2022.2107429
• 发表时间: 2022-07-28
• 期刊: JOURNAL OF COORDINATION CHEMISTRY
• 影响因子: 1.9
• 作者: Li，Runzi;Khan，Firoz Shah Tuglak;Hematian，Shabnam
• 通讯作者: Hematian，Shabnam