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

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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.