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Molecular electrocatalysis for oxygen reduction by cobalt porphyrins adsorbed at liquid/liquid interfaces
Journal of the American Chemical Society Cilt 132 ss. 2655-2662
Scopus Toplam 141 atıf DOI
Molecular electrocatalysis for oxygen reduction at a polarized water/1,2-dichloroethane (DCE) interface was studied, involving aqueous protons, ferrocene (Fc) in DCE and amphiphilic cobalt porphyrin catalysts adsorbed at the interface. The catalyst, (2,8,13,17-tetraethyl-3,7,12,18-tetramethyl-5-p- amino-phenylporphyrin) cobalt(II) (CoAP), functions like conventional cobalt porphyrins, activating O2 via coordination by the formation of a superoxide structure. Furthermore, due to the hydrophilic nature of the aminophenyl group, CoAP has a strong affinity for the water/DCE interface as evidenced by lipophilicity mapping calculations and surface tension measurements, facilitating the protonation of the CoAP-O2 complex and its reduction by ferrocene. The reaction is electrocatalytic as its rate depends on the applied Galvani potential difference between the two phases. © 2010 American Chemical Society.
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Biphasic water splitting by osmocene
Proceedings of the National Academy of Sciences of the United States of America Cilt 109 ss. 11558-11563
Scopus Havuzumuzda 42 atıf almış
The photochemical reactivity of osmocene in a biphasic waterorganic solvent system has been investigated to probe its water splitting properties. The photoreduction of aqueous protons to hydrogen under anaerobic conditions induced by osmocene dissolved in 1,2-dichloroethane and the subsequent water splitting by the osmocenium metal-metal dimer formed during H2 production were studied by electrochemical methods, UV-visible spectrometry, gas chromatography, and nuclear magnetic resonance spectroscopy. Density functional theory computations were used to validate the reaction pathways.
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Kurumlar (1)
École Polytechnique Fédérale de Lausanne Lausanne, Switzerland