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

该奖项的全部或部分资金来自《2021年美国救援计划法案》(公法117-2)。该项目由数学和物理科学局资助，设在化学系，北卡罗来纳大学格林斯伯勒分校的沙布南·赫马蒂安教授和她的研究团队将研究从光、空气和简单化合物中产生增值化学品的催化过程。随着对绿色化学和可持续化学设计的需求增加，使用光等绿色能源，而不是使用高能化学试剂，提供了一种节能的手段，将廉价和非活性的原材料转化为具有更高分子复杂性和价值的化学品。必须使用光催化剂捕捉光，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力(即氧气)作为绿色终端氧化剂也是非常有意义的。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，这种催化剂可以利用氧气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那些碳氢化合物，形成醇、环氧化物和其他有价值的化学产品。该项目还将为处于学术生活早期阶段的当地高中和社区大学学生以及通常无法获得这些机会的在家上学的高中生提供研究机会。该项目的主要目标是招收在STEM历史上代表性不足的学生，从而扩大他们在化学领域的参与度和留存率。该项目将专注于开发氧桥异双核系统，在该系统中，两种不同的金属中心，如铁和铜，通过氧化学通过氧配体连接在一起。然后将研究这类氧桥联组件的金属-氧键的光活化和整体催化活性。这种努力和氧桥联组件的模块化将提供对反应途径的更深层次的见解，以指导下一代有氧光催化剂的设计，以追求开发绿色氧化过程。该项目还将向在家上学的高中生和低收入的第一代社区大学生介绍研究机会，并将鼓励高中生，特别是女性和代表不足的少数族裔，早在二年级或三年级就参与研究经验。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。

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.