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Molecular Electrocatalysis for Oxygen Reduction by Cobalt Porphyrins Adsorbed at Liquid/Liquid Interfaces
(AMER CHEMICAL SOC, 2010) Su, Bin; Hatay, İmren; Trojanek, Antonin; Samec, Zdenek; Khoury, Tony; Gros, Claude P.; Barbe, Jean-Michel; Daina, Antoine; Carrupt, Pierre-Alain; Girault, Hubert H.
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-aminophenylporphyrin) cobalt(II) (CoAP), functions like conventional cobalt porphyrins, activating 02 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-O(2) complex and its reduction by ferrocene. The reaction is electrocatalytic as its rate depends on the applied Galvani potential difference between the two phases.