Participation in Negative Capacitance of Diffusion-Controlled Voltammograms of Hemin

Hemin in dimethyl sulfoxide solution has exhibited voltammograms controlled by diffusion at glassy carbon electrodes for slow scan rates, although it is adsorbed slightly. In contrast, voltammograms for high scan rates, v > 1 V s^-1, were governed by some kinds of kinetics judging from the scan rate dependence of peaks. The kinetics is close to that of a ferrocenyl derivative, in which the currents include the capacitive component with negative values. The capacitive one can be identified with the proportionality to the scan rates. The variation of the peak currents with v yielded -200 μF cm^-2. This negative value, being associated with the charge transfer reaction, makes cyclic voltammograms deviated downward from the diffusion-controlled behavior, resembling an irreversible reaction of the Butler-Volmer kinetics. Double layer capacitances are generally formed so that the applied electric field may be relaxed. The reduction of hemin forms a dipole coupled with a cation of the salt. The dipole orients from the electrode to the bulk, whereas the solvent dipoles orients in the opposite direction. Therefore, the capacitance is observed negatively. The capacitance determined by ac impedance took also negative values when the applied dc potential was only in the potential domain for the charge transfer. These complications can be avoided in electrocatalysis by use of such slow voltammetry as scan rates of 0.1 V s^-1 and ac frequency of 0.2 Hz.