Electrochemical switching of photoelectrochemical processes at CdS QDs and photosystem I-modified electrodes.

Photoactive inorganic CdS quantum dots (QDs) or the native photosystem I (PSI) is immobilized onto a pyrroloquinoline quinone (PQQ) monolayer linked to Au electrodes to yield hybrid relay/QDs (or photosystem) assemblies. By the electrochemical biasing of the electrode potential, the relay units are retained in their oxidized PQQ or reduced PQQH(2) states. The oxidized or reduced states of the relay units dictate the direction of the photocurrent (anodic or cathodic). By the cyclic biasing of the electrode potential between the values E ≥ -0.05 V and E ≤ -0.3 V vs Ag quasi-reference electrode (Ag QRE), retaining the relay units in the oxidized PQQ or reduced PQQH(2) states, the photocurrents are respectively switched between anodic and cathodic values. Different configurations of electrically switchable photoelectrochemical systems are described: (i) the PQQ/CdS QDs/(triethanolamine, TEOA) or PQQ/PSI/(ascorbic acid/dichlorophenolindophenol, DCPIP) systems, leading to anodic photocurrents; (ii) the PQQ/CdS QDs (or PSI)/(flavin adenine dinucleotide) systems, leading to cathodic photocurrents; (iii) the PQQ/CdS QDs (or PSI)/(O(2)) switchable systems, leading to cyclic anodic/cathodic switching of the photocurrents.