In:
Angewandte Chemie, Wiley, Vol. 135, No. 17 ( 2023-04-17)
Abstract:
The molecular structure, electrochemistry, spectroelectrochemistry and electrocatalytic oxygen reduction reaction (ORR) features of two Co II porphyrin(2.1.2.1) complexes bearing Ph or F 5 Ph groups at the two meso ‐positions of the macrocycle are examined. Single crystal X‐ray analysis reveal a highly bent, nonplanar macrocyclic conformation of the complex resulting in clamp‐shaped molecular structures. Cyclic voltammetry paired with UV/Vis spectroelectrochemistry in PhCN/0.1 M TBAP suggest that the first electron addition corresponds to a macrocyclic‐centered reduction while spectral changes observed during the first oxidation are consistent with a metal‐centered Co II /Co III process. The activity of the clamp‐shaped complexes towards heterogeneous ORR in 0.1 M KOH show selectivity towards the 4e − ORR pathway giving H 2 O. DFT first‐principle calculations on the porphyrin catalyst indicates a lower overpotential for 4e − ORR as compared to the 2e − pathway, consistent with experimental data.
Type of Medium:
Online Resource
ISSN:
0044-8249
,
1521-3757
DOI:
10.1002/ange.v135.17
DOI:
10.1002/ange.202218567
Language:
English
Publisher:
Wiley
Publication Date:
2023
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