On the mechanism of dioxygen electroreduction at transition metal meso‐tetrakis pyridyl porphyrins—a comparative spectroelectrochemical study

Popovici, S.; Leyffer, W.; Holze, R.

doi:10.1002/(sici)1099-1409(199904)3:4<265::aid-jpp131>3.3.co;2-5

Cited by 2 publications

(3 citation statements)

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“…This shift was considerably larger than the 150 mV shift found earlier for molecular oxygen reduction in the presence of the μ-oxo dimer of iron(III) tetramethoxyphenylporphine (FeTMPP) 2 O adsorbed on a Ag electrode . In a subsequent paper, Holze and co-workers also studied the SRRS of other metal ion complexes of TPyP, including NiTPyP and RuTPyP, adsorbed on a Ag electrode …”

Section: Introductionmentioning

confidence: 78%

“…29 In a subsequent paper, Holze and co-workers also studied the SRRS of other metal ion complexes of TPyP, including NiTPyP and RuTPyP, adsorbed on a Ag electrode. 30 The above studies have established the catalytic activity of the meso-substituted porphyrins toward the electrocatalytic reduction of dioxygen, and the work of Holze and co-workers [28][29][30] shows the utility of surface Raman spectroscopy in characterizing the porphyrin catalyst. Although a number of meso-substituted metal ion porphyrin catalysts have been investigated using surface Raman scattering, the chemical nature of adsorbed Fe-(III)TMPyP as an electrocatalyst has not been studied with this technique.…”

Section: Introductionmentioning

confidence: 99%

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Surface-Enhanced Resonance Raman Scattering and Voltammetry Study of the Electrocatalytic Reduction of Oxygen by the μ-Oxo Dimer of Iron(III) Tetra-4-N-methylpyridylporphyrin

et al. 2002

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In this study, surface-enhanced resonance Raman scattering, SERRS, and voltammetric techniques (cyclic voltammetry, rotating disk electrochemistry, and rotating ring disk electrochemistry) are used to elucidate the mechanism of oxygen reduction on a silver electrode with iron(III) tetra-4-N-methylpyridylporphyrin. The results indicate that after the oxidation reduction cycle at pH 10 and pH 4, the iron porphyrin is adsorbed on the silver surface as a high-spin, five-coordinated μ-oxo-bridged dimer. On the forward voltage scan, this dimer undergoes two successive one-electron reductions at about −0.3 and −0.5 V to form a high-spin fully reduced Fe(II) μ-oxo-bridged dimer. SERRS spectra show that the first electron transfer forms a mixed-valence Fe(II)−O−Fe(III) μ-oxo-bridged dimer system. At pH 2, only the high-spin reduced Fe(II) monomer is adsorbed on the surface. At pH 4 and pH 10, a shift in the reduction of the oxygen overpotential by approximately +150 mV is observed and the active catalyst in this process is attributed to the partially reduced μ-oxo dimer. A value of n ≈ 4 was calculated for the number of electrons involved in this catalytic reaction, and rotating ring disk voltammetry showed that only 10% stable hydrogen peroxide species is produced on the dimer-modified surface. These results are used to formulate a mechanism for the catalytic reduction of oxygen.

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Section: Introductionmentioning

confidence: 78%

Section: Introductionmentioning

confidence: 99%

Surface-Enhanced Resonance Raman Scattering and Voltammetry Study of the Electrocatalytic Reduction of Oxygen by the μ-Oxo Dimer of Iron(III) Tetra-4-N-methylpyridylporphyrin

et al. 2002

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“…Although many cathode catalysts using porphyrin have been intensively studied so far, few studies have focused on Rh(II) porphyrins despite their high reactivity. Holze and co-workers observed electrocatalytic O 2 reduction by Rh porphyrin …”

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Reversible Electrochemical Conversion between Rh(II) and Rh(III) States in Rh Porphyrin Adsorbed on Carbon Black

2004

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We have clearly demonstrated reversible cyclic voltammograms for the redox reaction between the Rh(II) and Rh(III) states in rhodium octaethylporphyrin [Rh(OEP)] adsorbed on carbon black in an acidic aqueous solution. The emergence of the reversible wave can be ascribed to the suppression of the undesirable reactions between two molecules of [Rh(II)(OEP)] because of its strong interaction with the carbon black. The generated [Rh(II)(OEP)] exhibits a potent catalytic O(2) reduction activity.

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On the mechanism of dioxygen electroreduction at transition metal meso‐tetrakis pyridyl porphyrins—a comparative spectroelectrochemical study

Cited by 2 publications

References 58 publications

Surface-Enhanced Resonance Raman Scattering and Voltammetry Study of the Electrocatalytic Reduction of Oxygen by the μ-Oxo Dimer of Iron(III) Tetra-4-N-methylpyridylporphyrin

Surface-Enhanced Resonance Raman Scattering and Voltammetry Study of the Electrocatalytic Reduction of Oxygen by the μ-Oxo Dimer of Iron(III) Tetra-4-N-methylpyridylporphyrin

Reversible Electrochemical Conversion between Rh(II) and Rh(III) States in Rh Porphyrin Adsorbed on Carbon Black

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