Journal
CHEMELECTROCHEM
Volume 1, Issue 9, Pages 1508-1515Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/celc.201402054
Keywords
density functional calculations; homogeneous catalysis; iron; porphyrins; redox mediator
Categories
Funding
- National Science Foundation [CHE-1012258, CHE-1265635]
- Department of Science and Technology (DST)/National Research Foundation (NRF) South African Research Chairs Initiative (SARChI)
- Direct For Mathematical & Physical Scien [1265635, 1012258] Funding Source: National Science Foundation
- Division Of Chemistry [1265635, 1012258] Funding Source: National Science Foundation
Ask authors/readers for more resources
The effects of different redox mediators on the oxygen reduction reaction (ORR) catalyzed by an iron porphyrin complex, iron(III) meso-tetra(N-methyl-4-pyridyl)porphine chloride [(FeTMPyP)-T-III], in 0.1 M triflic acid were investigated by cyclic voltammetry (CV) and spectroelectrochemistry in conjunction with density functional theory (DFT) calculations. The formal potentials of the (FeTMPyP)-T-III catalyst and the redox mediators, as well as the half-wave potentials for the ORR, were determined by CV in the absence and presence of oxygen in acidic solutions. UV/Vis spectroscopic and spectroelectrochemical studies confirmed that only the 2,2'-azino-bis(3-ethylbenzothiazioline-6-sulfonic acid) diammonium salt (C18H24N6O6S4) showed effective interactions with (FeTMPyP)-T-III during the ORR. DFT calculations suggested strong interaction between (FeTMPyP)-T-III and the C18H24N6O6S4 redox mediator. The redox mediator caused lengthening of the dioxygen iron bond, which thus suggested easier dioxygen reduction. Consistent results were observed in electrochemical impedance spectroscopic measurements for which the electron-transfer kinetics were also evaluated.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available