Effects of anions on the electrochemical behaviors of cobalt octaethylporphyrin adsorbed on HOPG

• WE examined the electrochemical behaviors of Co octaethylporphyrin (Co-OEP) on HOPG.
• Co-OEP exhibits reversible voltammograms at high potentials on HOPG in sulfuric acid.
• Some anions (halides and ClO4−) affect the redox behaviors.
• The high potential can be explained by the effect of ClO4−.
• Halides decreased CO oxidation by the Co porphyrin, while ClO4− did not.

The electrochemical behaviors of a cobalt porphyrin (Co octaethylporphyrin (Co-OEP)) adsorbed on highly oriented pyrolytic graphite (HOPG) were examined. Co-OEP on HOPG exhibits highly reversible voltammograms with a peak separation of almost zero. The redox potential of Co-OEP on HOPG in sulfuric acid was much higher than a previously reported value of Co-OEP on an edge plane electrode in perchloric acid. The high potential would be due to the instability of cationic trivalent state of Co on HOPG; hydrophilic trivalent state is not familiar with a hydrophobic surface of HOPG, and the interaction between cationic molecules causes positive shift in the redox potential. Certain anions (Cl−, Br−and ClO4−) cause a negative shift of midpoint potential of Co-OEP, since they counteract the positive charge of trivalent Co in Co-OEP. The dissociation constants of Co-OEP-Cl and Co-OEP-Br were determined from the potential shift. The constants indicate that Br−coordinates on Co-OEP more strongly than Cl−. ClO4−has a different effect on the redox behaviors of Co-OEP than halides. While the oxidation of CO oxidation by Co-OEP was suppressed by the coordination of these halides, ClO4−did not significantly decrease the CO oxidation current, but rather decreased the overpotential for CO oxidation. These results suggest that halides coordinate on trivalent Co-OEP, while ClO4−interacts with positive charge of trivalent Co-OEP without coordination.

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