Study of the factors affecting the photoelectrode characteristics of a perylene/phthalocyanine bilayer working in the water phase

Some types of phthalocyanines (MPc (M = H2, Cu, or Zn), a p-type semiconductor) were used in combination with 3,4,9,10-perylenetetracarboxyl-bisbenzimidazole (PTCBI, an n-type semiconductor), with which those photoelectrode characteristics in the water phase were investigated in terms of kinetics. Each film of the PTCBI/MPc bilayer functioned as a photoanode, where the photoinduced oxidation of thiol occurs at the MPc/water interface along with the hole conduction through the MPc layer. The holes originate on account of the photophysical events in the p/n interior, involving the charge separation of excitons at the p/n interface. The typical photoelectrochemical characteristic in the PTCBI/MPc photoanodes involved a transient photocurrent occurring in the initial stage under illumination (under potentiostatic conditions): thereafter, it attained a steady state. Moreover, both the initial spiky photocurrents and the steady-state photocurrents exhibited saturation at higher concentrations. An analysis with photoelectrode kinetics was performed by assuming an adsorption step prior to a rate-limiting charge transfer step, where equations were applied to photocurrents based on the Langmuir adsorption equilibrium. The kinetic analyses evidently showed that the photoanodic reactions are kinetically dominated by the charge transfer between MPc and thiol, where the overall kinetics for thiol oxidation decreases in the following order: H2Pc > ZnPc > CuPc; that is, it appeared that H2Pc acts as the more efficient photofunctional interface capable of oxidation in the water phase when PTCBI was concurrently employed as an electron conductor. Considering that the photocurrent generated is proportional to the surface concentration of thiol (Γ) at the MPc as well as the intrinsic oxidation rate (cf., ZnPc > H2Pc ∼ CuPc), the higher efficiency in the output at the H2Pc surface was attributed to an exceptionally high Γ (i.e., from the kinetic analyses, the Γ value at the H2Pc surface was also inferred to be 2–3 times higher than that at the other MPcs). Through the present kinetic analysis, it also revealed that the activity for thiol oxidation taking place at Pc ring is comparable to that at the conventional active catalysts (i.e., polycarboxyphthalocyaninato Co(II) and Fe(III)) where a central metal is an active site.