Department of Plant Sciences, The Alexander Silberman Institute of Life Sciences, The Hebrew University of Jerusalem, Jerusalem 91904, Israel.
ACS Nano. 2012 Oct 23;6(10):9258-66. doi: 10.1021/nn3037286. Epub 2012 Oct 12.
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.
将光活性无机 CdS 量子点 (QDs) 或天然光系统 I (PSI) 固定在连接到 Au 电极的吡咯并喹啉醌 (PQQ) 单层上，以得到混合继电器/QD（或光系统）组件。通过对电极电势进行电化学偏置，可以使继电器单元保持在其氧化的 PQQ 或还原的 PQQH(2) 状态。继电器单元的氧化或还原状态决定了光电流的方向（阳极或阴极）。通过在 E ≥ -0.05 V 和 E ≤ -0.3 V 与 Ag 准参比电极 (Ag QRE) 之间的电极电势的循环偏置，将继电器单元保持在氧化的 PQQ 或还原的 PQQH(2) 状态，光电流分别在阳极和阴极值之间切换。描述了不同配置的电可切换光电化学系统：(i) PQQ/CdS QDs/(三乙醇胺，TEOA) 或 PQQ/PSI/(抗坏血酸/二氯酚靛酚，DCPIP) 系统，导致阳极光电流；(ii) PQQ/CdS QDs（或 PSI)/(黄素腺嘌呤二核苷酸) 系统，导致阴极光电流；(iii) PQQ/CdS QDs（或 PSI)/(O(2)) 可切换系统，导致光电流的循环阳极/阴极切换。
