Electrochemically Promoted Organic Isomerization Reactions at Polymer Electrolyte Fuel Cell Cathodes

A significant cost of bench-top synthesis of small molecule target compounds is in the purchase and disposal of solvents for use in carrying out the reactions and purification of the raw product. The working electrode of a proton exchange membrane fuel cell provides a surface of tunable acidity capable of catalyzing certain reactions. This technique has the added advantage of not only providing a solvent-free environment for organic synthesis, but also increases the reaction kinetics. The progress of each reaction is monitored through the use of a fuel cell capable of obtaining operando infrared spectra. This cell was also used in study of temperature dependent Stark tuning rates of adsorbed CO on a Pt electrode. The study demonstrated Nafion interaction with the Pt surface and through the use of polarization modulated infrared reflection adsorption spectroscopy PM-IRRAS, attenuated total reflectance ATR spectroscopy, and density functional theory DFT the functional groups responsible for this interaction were identified and model for Nafion adsorption was derived and is in press in the Journal of the American Chemical Society.