Rational Design and Mechanistic Understanding of Macrocyclic Catalysts for CO2 Reduction Featuring Redox-Active Ligands

About This Grant

With the support of the Chemical Catalysis Program in the Division of Chemistry, Professor Jurss of the University of Mississippi is studying the development of new catalysts capable of transforming carbon dioxide into value-added chemicals. Carbon dioxide is generally viewed as a waste product that is made when burning carbon-based fuels, such as coal, oil, and natural gas. However, carbon dioxide could be used as a feedstock to regenerate fuels or commodity chemicals using sunlight or electricity to drive this process. The conversion of carbon dioxide into desirable products is often energy-intensive and requires catalysts to facilitate the reaction; catalysts are compounds added to make reactions more efficient by introducing lower energy pathways to product formation. Dr. Jurss will develop more effective catalysts based on innovative design strategies to take carbon dioxide from unwanted waste to useful products, which has important implications for national security and the economy. During this project, Dr. Jurss will actively recruit, mentor, and train graduate students, undergraduate students, and Mississippi high school students through a hands-on research program that will promote careers in science, technology, engineering, and mathematics (STEM). The education and training of students in chemistry, and STEM more broadly, will allow the United States to maintain and grow a highly skilled and globally competitive workforce, and remain a leader in technological development and scientific advancement. With the support of the Chemical Catalysis Program in the Division of Chemistry, Professor Jurss of the University of Mississippi will develop new catalysts featuring tunable redox-active ligands that target ligand-based carbon dioxide activation. Current molecular catalysts are often limited by high overpotentials, poor product selectivity, and/or low stability. This work will address these shortcomings through hypothesis-driven design and development of macrocyclic catalysts for carbon dioxide reduction by controlling the metal-ligand redox chemistry and promoting ligand-based substrate activation. This underexplored mode of carbon dioxide activation will be investigated as a means to move beyond the common two-electron reduction chemistry (i.e. carbon dioxide reduction to carbon monoxide or formate) that dominates this field to more reduced carbon products, such as methane. Appropriate functionality will be added to the ligand backbone to introduce hydrogen-bonding interactions and/or proton relays near the active site to enhance substrate binding and conversion. Mechanistic insight will be gained through electrochemical and photochemical reactivity studies, spectroscopy, and structure-activity relationships. This project will also afford research opportunities in the critically important area of catalysis for graduate, undergraduate, and Mississippi high school students. 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.