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

在这个由化学系化学结构、动力学和机理B计划资助的职业项目中，爱荷华大学化学系的Scott Daly教授正在开发二氧化碳电化学转化的新方法。二氧化碳是化石燃料燃烧的副产品，很容易获得。它转化为一氧化碳等其他分子可能会导致高密度液体燃料的发展。因此，人们正在积极寻求将二氧化碳转化为其他分子的有效方法。Scott Daly教授的方法是基于金属-配体的协作性和氧化还原的非无辜配体的耦合。他的方法的一个优点是，它不需要使用昂贵的金属。在他的教育计划中，斯科特·戴利教授正在开发“化学排”--这是一个辅导和推广计划，旨在帮助退伍军人学生在爱荷华大学的大规模招生化学课程中取得成功。作为一名退伍军人，斯科特·戴利教授处于有利地位，将在这一努力中产生重大影响。含有邻苯二胺亚单位的氧化还原活性四齿配体能够经历两次连续的电子转移事件。Scott Daly教授正在研究这种以配体为中心的氧化还原活性与金属-配体合作(MLC)结合的耦合，以实现利用富含稀土的第一排过渡金属高效地将二氧化碳电化学还原为一氧化碳。具有修饰的给体取代基和结构的氧化还原活性配体正在被制备，以确定促进MLC结合的二氧化碳的电化学还原的配体变化。含有氧化还原不活跃的四齿配体的金属络合物被用作基准，以阐明配体氧化还原化学在通过MLC结合的电化学二氧化碳还原中的作用。将点燃烧来源的二氧化碳转化为一氧化碳，一氧化碳是制造高密度液体燃料(如甲醇)的重要原料，这可能会减少我们对化石燃料的依赖，从而减少二氧化碳排放。

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.