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RESEARCH PRODUCT
Self-Assembled Molecular Rafts at Liquid|Liquid Interfaces for Four-Electron Oxygen Reduction
Delphine SchamingTomáš ZimmermannHai-jun XuJiri VanicekHubert H. GiraultClaude P. GrosPierre-françois Marie BrevetJean-michel BarbeAstrid J. OlayaHirohisa Nagatanisubject
inorganic chemicals2Nd-Harmonic Generationchemistry.chemical_elementPhotochemistryBiochemistryOxygenCatalysisCatalysischemistry.chemical_compoundWater-Soluble PorphyrinsColloid and Surface ChemistryCobalt Porphyrinsheterocyclic compoundsLiquid/Liquid Interface2Nd DerivativesEnergyDioxygenPolarizable Continuum ModelGeneral ChemistryPorphyrinRadical CationchemistryRadical ionSurface second harmonic generationDensity functional theoryImmiscible Electrolyte-SolutionsCobaltTetrathiafulvalenedescription
The self-assembly of the oppositely charged water-soluble porphyrins, cobalt tetramethylpyridinium porphyrin (CoTMPyP(4+)) and cobalt tetrasulphonatophenyl porphyrin (CoTPPS(4-)), at the interface with an organic solvent to form molecular "rafts", provides an excellent catalyst to perform the interfacial four-electron reduction of oxygen by lipophilic electron donors such as tetrathiafulvalene (TTF). The catalytic activity and selectivity of the self-assembled catalyst toward the four-electron pathway was found to be as good as that of the Pacman type cofacial cobalt porphyrins. The assembly has been characterized by UV-visible spectroscopy, Surface Second Harmonic Generation, and Scanning Electron Microscopy. Density functional theory calculations confirm the possibility of formation of the catalytic CoTMPyP(4+)/ CoTPPS(4-) complex and its capability to bind oxygen.
| year | journal | country | edition | language |
|---|---|---|---|---|
| 2011-12-15 |