American Chemical Society
ja3c14549_si_001.pdf (5.72 MB)

Metal-Free Homogeneous O2 Reduction by an Iminium-Based Electrocatalyst

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journal contribution
posted on 2024-03-15, 12:40 authored by Emma N. Cook, Anna E. Davis, Michael K. Hilinski, Charles W. Machan
The oxygen reduction reaction (ORR) is important for alternative energy and industrial oxidation processes. Herein, an iminium-based organoelectrocatalyst (im+) for the ORR with trifluoroacetic acid as a proton source in acetonitrile solution under both electrochemical and spectrochemical conditions using decamethylferrocene as a chemical reductant is reported. Under spectrochemical conditions, H2O2 is the primary reaction product, while under electrochemical conditions H2O is produced. This difference in selectivity is attributed to the interception of the free superoxide intermediate under electrochemical conditions by the reduced catalyst, accessing an alternate inner-sphere pathway.