DC and AC voltammetry of a free-base porphyrin adsorbed onto basal-plane graphite under acidic conditions: An example of a close to ideal reversible two-electron surface-confined redox process at sub-monolayer coverages

The free-base porphyrin, 5,10,15,20-tetrakis(1-methyl-4-pyridyl)-21H,23H-porphine (H2TMPyP), adsorbs onto a basal-plane graphite electrode. Under DC cyclic voltammetric conditions, the fully protonated dication, [H4TMPyP(0)]2+, undergoes an apparently close to ideal surface-confined two-electron reduction to the neutral [H4TMPyP(-II)] species when the supporting electrolyte consists of aqueous 1 M HCl and 1 M NaCl and coverages are sub-monolayer. The reversible potential calculated from the average of the oxidation and reduction peak potentials is 0.138 ± 0.002 V (vs Ag/AgCl, 3 M NaCl) whilst their separation ΔEp, approaches 0 mV at slow scan rates, as expected theoretically for an ideal surface-confined electron transfer process. Comparisons of simulated and experimental data imply that the increase in ΔEp observed at scan rates above 10 V s−1 is consistent with uncompensated Ohmic IRu drop effects, and not limitations imposed by electron transfer kinetics. Analysis of fundamental and higher harmonic components derived from large-amplitude sine-wave AC voltammetry is consistent with a very fast electron transfer rate constant, k0, in excess of 106 s−1 for the overall two-electron process. However, careful comparison with AC theory highlights minor levels of non-ideality not attributable to purely capacitative background or uncompensated resistance effects. These are particularly evident when greater than monolayer surface coverages are employed. It is likely that subtle contributions from heterogeneity in the adsorbed layer and complexities in the reaction mechanism are present in this close to ideal surface-confined process, but they are more readily detected under conditions of large-amplitude Fourier transformed AC cyclic voltammetry than with the conventionally used DC cyclic format.