Cook Emma N, Davis Anna E, Hilinski Michael K, Machan Charles W
Department of Chemistry, University of Virginia, PO Box 400319, Charlottesville, Virginia 22904-4319, United States.
J Am Chem Soc. 2024 Mar 27;146(12):7931-7935. doi: 10.1021/jacs.3c14549. Epub 2024 Mar 15.
The oxygen reduction reaction (ORR) is important for alternative energy and industrial oxidation processes. Herein, an iminium-based organoelectrocatalyst () 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, HO is the primary reaction product, while under electrochemical conditions HO 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.
氧还原反应（ORR）对于替代能源和工业氧化过程至关重要。本文报道了一种基于亚胺鎓的有机电催化剂（），在电化学和光谱化学条件下，以十甲基二茂铁作为化学还原剂，在乙腈溶液中以三氟乙酸作为质子源用于ORR。在光谱化学条件下，HO是主要反应产物，而在电化学条件下会产生HO。这种选择性差异归因于在电化学条件下还原的催化剂拦截了游离超氧中间体，从而进入了另一条内球途径。
