Anion controlled selectivity in oxygen reduction catalysed by a dinuclear cobalt N,O-Schiff base complex
A new dinuclear cobalt complex selectively catalyses 4e<sup>-</sup> reduction of O<sub>2</sub> to water in methanol containing acetic acid. Its TOF of 0.031 s<sup>-1</sup> and overpotential of 690 mV outperform the few previous Co N,O-chelate based catalysts for the 4e<sup>-</sup> ORR. Replacing acetic acid with NH<sub>4</sub>PF<sub>6</sub> as proton source induces a complete and unprecedented switch to the H<sub>2</sub>O<sub>2</sub> producing 2e<sup>-</sup> pathway. Mechanistic studies suggest a peroxo intermediate for both pathways, with acetate coordination/decoordination determining the destination of a key electron transfer.
Authors
- Samuel Jarvis (ORCID: https://orcid.org/0000-0003-4031-1519)
- John Fielden (ORCID: https://orcid.org/0000-0001-5963-7792)
- Adam Brookfield (ORCID: https://orcid.org/0000-0001-5864-0041)
- Carl E. James
- H. Willoughby Ellis
- Jessica E Swindells
- Richa Arjariya
Institutions
- University of East Anglia (GB)
- Norwich Research Park (GB)
- University of Manchester (GB)
- Lancaster University (GB)
Publication Details
- Journal
- Chemical Communications
- Published
- 2025-01-01
- DOI
- https://doi.org/10.1039/d5cc02476e
- Primary Topic
- Electrocatalysts for Energy Conversion
- Type
- article
- Field-Weighted Citation Impact
- 0.00
Funders
- Engineering and Physical Sciences Research Council