Electrocatalytic Oxidation of Alcohols, Amines, and Carbon-Carbon Bonds

University Of Rochester, Rochester NY

Investigators

Abstract

With funding from the Chemical Catalysis Program of the Division of Chemistry, Dr. William D. Jones of the University of Rochester is developing new catalytic materials capable of removing hydrogen from organic molecules to make more valuable products. In this new method, hydrogen is transferred from the organic molecule to a carrier molecule using a metal catalyst. The carrier molecules are then recycled many times. Dr. Jones is studying the individual steps of the reaction cycle. These catalytic reactions have applications in the synthesis of pharmaceuticals and may also provide a better understanding of how electrical energy from hydropower or wind turbines could be captured and stored for later use on demand. Dr. Jones is engaged in outreach activities to inform the public about novel new concepts for energy storage and organic compound synthesis. He and his group participate in public radio shows such as WXXI Connections, and speak on television news programs. The researchers include both undergraduate and graduate students who are being trained to solve difficult technical problems of broad societal interest. This research advances the national health and prosperity by contributing to technical innovations in the pharmaceuticals and renewable energy industries. Dr. Jones is developing homogeneous transition metal catalysts that can be used to dehydrogenate alcohols, amines, and heterocycles electrochemically. The group is studying the use of new and known catalysts in combination with quinones as electron transfer mediators, as the latter have the ability to undergo reversible electrochemical reduction and oxidation, and show promise as mediators with transition metal catalysts. The group is examining stoichiometric reactions for alcohol and amine dehydrogenation with various quinones as hydrogen acceptors. The group is also developing electrochemical recycling of the hydroquinone hydrogen acceptors. By proper choice of solvent and electrolyte, an electrochemical route for dehydrogenations is being extended to substrates that can produce heterocycles such as indoles and quinolones. Finally, this electrochemical method is being used in applications for dehydrogenation of activated C-C bonds to generate oxidized organic products that serve as building blocks in the chemical and pharmaceutical industry. This work has the potential to occur with dihydrogen as the only byproduct, using electrochemistry to provide the driving force for the thermodynamically uphill reaction. This work is focusing on the use of these catalysts in organic synthesis, but also can find applications in hydrogen storage, and fuel cells. The students engaged in this research are learning advanced techniques for handling sensitive compounds and therefore are being trained as Highly Qualified Personnel (HQP) for work in advanced industrial research labs. 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.