Issue 3, 2022

Influence of the spatial distribution of copper sites on the selectivity of the oxygen reduction reaction

Abstract

Moving towards a hydrogen economy raises the demand for affordable and efficient catalysts for the oxygen reduction reaction. Cu-bmpa (bmpa = bis(2-picolyl)amine) is shown to have moderate activity, but poor selectivity for the 4-electron reduction of oxygen to water. To enhance the selectivity towards water formation, the cooperative effect of three Cu-bmpa binding sites in a single trinuclear complex is investigated. The catalytic currents in the presence of the trinuclear sites are lower, possibly due to the more rigid structure and therefore higher reorganization energies and/or slower diffusion rates of the catalytic species. Although the oxygen reduction activity of the trinuclear complexes is lower than that of mononuclear Cu-bmpa, the selectivity of the copper mediated oxygen reduction was significantly enhanced towards the 4-electron process due to a cooperative effect between three copper centers that have been positioned in close proximity. These results indicate that the cooperativity between metal ions within biomimetic sites can greatly enhance the ORR selectivity.

Graphical abstract: Influence of the spatial distribution of copper sites on the selectivity of the oxygen reduction reaction

Supplementary files

Article information

Article type
Paper
Submitted
28 9月 2021
Accepted
25 11月 2021
First published
21 12月 2021
This article is Open Access
Creative Commons BY license

Dalton Trans., 2022,51, 1206-1215

Influence of the spatial distribution of copper sites on the selectivity of the oxygen reduction reaction

N. W. G. Smits, D. Rademaker, A. I. Konovalov, M. A. Siegler and D. G. H. Hetterscheid, Dalton Trans., 2022, 51, 1206 DOI: 10.1039/D1DT03296H

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