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Cobalt porphine (CoP) dissolved in the organic phase of a biphasic system is used to catalyze O2 reduction by an electron donor, ferrocene (Fc). Using voltammetry at the interface between two immiscible electrolyte solutions (ITIES), it is possible to drive this catalytic reduction at the interface as a function of the applied potential difference, where aqueous protons and organic electron donors combine to reduce O2. The current signal observed corresponds to a proton-coupled electron transfer (PCET) reaction, as no current and no reaction can be observed in the absence of either the aqueous acid, CoP, Fc, or O2.

Oxygen reduction catalyzed by cofacial metalloporphyrins at the 1,2-dichlorobenzene-water interface was studied with two lipophilic electron donors of similar driving force, 1,1'-dimethylferrocene (DMFc) and tetrathiafulvalene (TTF). The reaction produces mainly water and some hydrogen peroxide, but the mediator has a significant effect on the selectivity, as DMFc and the porphyrins themselves catalyze the decomposition and the further reduction of hydrogen peroxide. Density functional theory calculations indicate that the biscobaltporphyrin, 4,5-bis[5-(2,8,13,17-tetraethyl-3,7,12,18-tetramethylporphyrinyl)]-9,9-dimethylxanthene, Co-2(DPX), actually catalyzes oxygen reduction to hydrogen peroxide when oxygen is bound on the "exo" side ("dock-on") of the catalyst, while four-electron reduction takes place with oxygen bound on the "endo" side ("dock-in") of the molecule. These results can be explained by a "dock-on/dock-in" mechanism. The next step for improving bioinspired oxygen reduction catalysts would be blocking the "dock-on" path to achieve selective four-electron reduction of molecular oxygen.