Molecular Catalysis of O2 Reduction by Iron Porphyrins in Water: Heterogeneous versus Homogeneous Pathways
- 16 October 2015
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 137 (42) , 13535-13544
Abstract
Despite decades of active attention, important problems remain pending in the catalysis of dioxygen reduction by iron porphyrins in water in terms of selectivity and mechanisms. This is what happens, for example, for the distinction between heterogeneous and homogeneous catalysis for soluble porphyrins, for the estimation of H2O2/H2O product selectivity, and for the determination of the reaction mechanism in the two situations. With water-soluble iron tetrakis(N-methyl-4-pyridyl)porphyrin as an example, procedures are described that allow one to operate this distinction and determine the H2O2/H2O product ratio in each case separately. It is noteworthy that, despite the weak adsorption of the iron(II) porphyrin on the glassy carbon electrode, the contribution of the adsorbed complex to catalysis rivals that of its solution counterpart. Depending on the electrode potential, two successive catalytic pathways have been identified and characterized in terms of current–potential responses and H2O2/H2O selectivi...Keywords
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