Photoinduced hydrogen production using a multilayered molecular assembly composed of zinc tetraphenylporphine and Nafion® membrane

A photoinduced proton reduction to produce H₂ was found to take place in the system using zinc tetraphenylporphine (ZnTPP) incorporated into a Nafion® membrane coated on a platinum electrode (denoted as Pt/Nf[ZnTPP]). When visible light (λ > 390 nm) was irradiated on the Pt/Nf[ZnTPP] system, a photocurrent was generated under applied potentials below −0.10 (v. Ag/AgCl). The action spectrum for the photocurrent agreed with the absorption spectrum of the Nf[ZnTPP] membrane, showing that the present photochemical process is induced on light absorption by the ZnTPP. By measuring the emission decay of ZnTPP under the photoelectrochemical conditions, it was exhibited that the emission from the singlet excited ZnTPP is quenched by the cathodic potentials. The amount of the H₂ produced increased with the cathodic potentials. These results indicated that, in the photochemical primary process, a reductive quenching takes place by electron injection from the Pt electrode to the singlet excited ZnTPP forming ZnTPP^.–, subsequently leading to the H₂ formation by a bimolecular catalysis of the ZnTPP. Copyright © 2000 John Wiley & Sons, Ltd.