CAREER:CAS:Confined Nano-Environments for the Stabilization of Molecular Electrocatalysts

在这个CAREER项目中，由化学部化学结构、动力学和机制B项目和刺激竞争研究的既定项目（EPSCoR）共同资助，路易斯安那州立大学化学系的Noemie Elgrishi博士正在揭示氧化还原活性分子在密闭空间中封装后电子转移变化的规律。该项目的长期目标是开发一种策略，通过封装在纳米容器中来控制形成燃料的分子电催化剂的稳定性、选择性和活性。该项目在能源存储以及依赖于分子催化剂的任何其他电催化过程中都有应用。该项目位于无机化学和分析化学的交汇处。它非常适合培养本科生和研究生广泛的合成和表征技术，包括电化学，这是一个关键的挑战。能源技术的核心依赖于电力的生产和储存，而电化学知识是其基础。该教育计划将通过在大一化学课上的模块和课堂演示，以及在专门的高级电分析化学课上实施实验室“实地考察”来改善本科电化学教育，从而进一步促进这一目标。通过外展计划，Elgrishi博士将继续与社区互动，并通过开发简单的动手电化学演示来促进关键人群对STEM职业的兴趣。这些研究的目的是增加我们对有限空间中电子转移的基本理解；这是进一步发展电催化的关键知识。所选择的系统由分子金属笼组成，其中封装了电活性配合物和催化剂。电子转移将使用电分析和光谱技术，在电子隧穿和跳跃条件下进行探测。对电子转移后影响包封配合物命运的参数也将进行研究。该项目的长期目标是开发一种策略，通过封装在纳米容器中来控制形成燃料的分子电催化剂的稳定性、选择性和活性。总的来说，这些研究将提高对固定化后燃料形成催化剂的理解。了解位点分离、控制包封和孔径等基本过程的影响将有助于弥合均相和非均相分子催化之间的差距。该项目将为进一步研究电催化剂第二配位球的合理裁剪铺平道路。这些研究有可能影响分子电催化剂发挥关键作用的许多化学领域，包括能量存储应用。该奖项反映了美国国家科学基金会的法定使命，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。

In this CAREER project, co-funded by the Chemical Structure, Dynamics & Mechanism B Program of the Chemistry Division and the Established Program to Stimulate Competitive Research (EPSCoR), Dr. Noemie Elgrishi of the Department of Chemistry at Louisiana State University is uncovering the rules governing changes in electron transfer after encapsulation of redox active molecules in confined spaces. The long-term goal of this project is to develop a strategy to control the stability, selectivity, and activity of fuel-forming molecular electrocatalysts through encapsulation in nano-containers. This project has applications in energy storage as well as any other electrocatalytic process relying on molecular catalysts. The project lies at the interface of inorganic and analytical chemistry. It is well suited to train undergraduate and graduate students in a wide range of synthesis and characterization techniques, including electrochemistry which is a key challenge. At their core, energy technologies rely on electricity production and storage, for which electrochemical knowledge is fundamental. The educational plan will further contribute to this goal through improving undergraduate electrochemical education through modules and in-class demonstrations in freshman chemistry classes as well as through the implementation of lab “field trips” in a dedicated an upper-level electroanalytical chemistry class. Through the outreach plan, Dr. Elgrishi will continue engaging with the community and promote interest in STEM careers to key demographics by developing simple hands-on electrochemistry demonstrations. These studies are aimed at increasing our fundamental understanding of electron transfer in confined spaces; this is critical knowledge to further the development of electrocatalysis. The systems chosen are composed of molecular metallo-cages within which electro-active complexes and catalysts are encapsulated. Electron transfer will be probed using electroanalytical and spectroscopic techniques, both in electron tunneling and hopping conditions. The parameters impacting the fate of the encapsulated complexes after electron transfer will also be investigated. The long-term goal of this project is to develop a strategy to control the stability, selectivity, and activity of fuel-forming molecular electrocatalysts through encapsulation in nano-containers. Collectively, these investigations will provide an improved understanding of fuel-forming catalysts upon immobilization. Understanding the effect of the fundamental processes of site isolation, controlled encapsulation, and pore size will help bridge the gap between homogeneous and heterogeneous molecular catalysis. This project will pave the way for further studies on rational tailoring of the second coordination spheres of electrocatalysts. These studies have the potential to impact the many areas of chemistry in which molecular electrocatalysts play a key role, including for energy storage applications.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.