Anion controlled selectivity in oxygen reduction catalysed by a dinuclear cobalt N,O-Schiff base complex †

James, Charles A. and Swindells, Jessica E. and Ellis, Harry and Arjariya, Richa and Jarvis, Samuel P. and Brookfield, Adam and Fielden, John (2025) Anion controlled selectivity in oxygen reduction catalysed by a dinuclear cobalt N,O-Schiff base complex †. Chemical Communications. ISSN 1359-7345

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Abstract

A new dinuclear cobalt complex selectively catalyses 4e− reduction of O2 to water in methanol containing acetic acid. Its TOF of 0.031 s−1 and overpotential of 690 mV outperform the few previous Co N,O-chelate based catalysts for the 4e− ORR. Replacing acetic acid with NH4PF6 as proton source induces a complete and unprecedented switch to the H2O2 producing 2e− pathway. Mechanistic studies suggest a peroxo intermediate for both pathways, with acetate coordination/decoordination determining the destination of a key electron transfer.

Item Type:
Journal Article
Journal or Publication Title:
Chemical Communications
Uncontrolled Keywords:
/dk/atira/pure/subjectarea/asjc/2500/2505
Subjects:
?? materials chemistrysurfaces, coatings and filmsmetals and alloysceramics and compositeschemistry(all)catalysiselectronic, optical and magnetic materials ??
ID Code:
231310
Deposited By:
Deposited On:
07 Aug 2025 09:15
Refereed?:
Yes
Published?:
Published
Last Modified:
08 Aug 2025 04:15