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


ABSTRACT: 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.

SUBMITTER: Cook EN 

PROVIDER: S-EPMC10979433 | biostudies-literature | 2024 Mar

REPOSITORIES: biostudies-literature

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Metal-Free Homogeneous O<sub>2</sub> Reduction by an Iminium-Based Electrocatalyst.

Cook Emma N EN   Davis Anna E AE   Hilinski Michael K MK   Machan Charles W CW  

Journal of the American Chemical Society 20240315 12


The oxygen reduction reaction (ORR) is important for alternative energy and industrial oxidation processes. Herein, an iminium-based organoelectrocatalyst (<b>im</b><sup><b>+</b></sup>) 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, H<sub>2</sub>O<sub>2</sub> is the primary reaction product, while under elect  ...[more]

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