Self-Assembled Molecular Rafts at Liquid|Liquid Interfaces for Four-Electron Oxygen Reduction

The self-assembly of the oppositely charged watersoluble porphyrins, cobalt tetramethylpyridinium porphyrin (CoTMPyP4+) and cobalt tetrasulphonatophenyl porphyrin (CoTPPS4−), 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 CoTMPyP4+/ CoTPPS4− complex and its capability to bind oxygen.


Published in:
Journal of the American Chemical Society, 134, 498-506
Year:
2012
Keywords:
Laboratories:




 Record created 2012-02-07, last modified 2018-01-28

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