Electron transfer events are commonly considered in light of the transfer of charge. But, electrons also have properties of spin. Electron spins interact with magnetic fields. In the presence of a localized magnetic field, electron transfer rates of electrochemical reactions change. Correlations between a redox species’ number of unpaired electrons and the change in electron transfer rate have been found.

Many important reactions that include the oxygen reduction reaction (ORR), hydrogen evolution reaction (HER), and carbon dioxide reduction have been shown to be kinetically limited. ORR limits performance of many fuel cell and air batteries. Increased rates of HER facilitate energy generation. The presence of lanthanides at electrode surfaces can mediate the rates of such important reactions. For example, Ytterbium triflate extracted into Nafion on an electrode in acetonitrile increases oxygen reduction currents by 15%.

Despite largely similar properties, lanthanide magnetic properties are diverse because the number of unpaired electrons in the d orbitals ranges from 0 to 7. Voltammetry for lanthanides extracted into Nafion films on electrodes undertaken in the presence of some of these species will be presented. Correlations between lanthanides (and their spin and magnetic properties) and the type and magnitude of effects on important reactions will be discussed.