CAREER: SusChEM: Coupling Earth-Abundant Metal-Ligand Cooperativity with Redox Non-Innocent Ligands for Electrochemical Carbon Dioxide Reduction

University Of Iowa, Iowa City IA

Investigators

Abstract

In this CAREER project funded by the Chemical Structure, Dynamics & Mechanisms B Program of the Chemistry Division, Professor Scott Daly of the Department of Chemistry at the University of Iowa is developing new methods for the electrochemical conversion of carbon dioxide. Carbon dioxide, a by-product of fossil fuel combustion, is readily available. Its conversion into other molecules such as carbon monoxide may lead to the development of high-density liquid fuels. As a result, effective ways of converting carbon dioxide into other molecules are being actively pursued. Professor Scott Daly's approach is based on the coupling of metal-ligand cooperativity with redox non-innocent ligands. One advantage of his approach is that it does not require the use of expensive metals. For his educational plan, Professor Scott Daly is developing the "Chemistry Platoon" - a tutoring and outreach program created to help student veterans to succeed in large-enrollment chemistry courses at the University of Iowa. Being a military veteran, Professor Scott Daly is well positioned to make significant impacts in this endeavor. Redox-active tetradentate ligands containing o-phenylenediamine sub-units are capable of undergoing two sequential electron transfer events. Professor Scott Daly is studying the coupling of this ligand-centered redox-activity with metal-ligand cooperative (MLC) binding to achieve efficient electrochemical reduction of carbon dioxide to carbon monoxide with earth-abundant, first-row transition metals. Redox-active ligands with modified donor substituents and structures are being prepared to identify ligand variations that promote electrochemical reduction of MLC-bound carbon dioxide. Metal complexes containing redox-inactive tetradentate ligands are being used as benchmarks to elucidate the role of ligand redox chemistry in electrochemical carbon dioxide reduction via MLC binding. Converting carbon dioxide from point combustion sources into carbon monoxide, an important feedstock for high-density liquid fuels such as methanol, may decrease our fossil fuel reliance so that carbon dioxide emissions can be reduced.