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Photo-excitation of photosystem (PS) I complexes at an SnO2/electrolyte interface yielded an anodic photocurrent in the presence of methyl or benzyl viologen. In sharp contrast to ordinary spectral sensitization of semiconductor electrodes, the photocurrent appeared at potentials far negative of the flatband potential of SnO2, the photocurrent formed a bell-shaped curve against the potential, and the peak potential shifted in a Nernstian manner as a function of the viologen concentration. These results suggest an isoenergetic electron transfer from the reduced form of mediator (viologen) bound just beneath the PS I complex surface.

Photoelectrochemical Behavior of Photosystem I Complex in the Presence of a Viologen as Mediator at SnO2 Electrode