Effects of Surface Charges and Surface States of Chemically Modified Cadmium Sulfide Nanoparticles Immobilized to Gold Electrode Substrate on Photoinduced Charge Transfers

Cadmium sulfide nanoparticles (Q-CdS) modified with 2-mercaptoethanesulfonate and 2-aminoethanethiol in a molar ratio of 2:1 were covalently immobilized onto an Au surface covered with a self-assembled monolayer of 3,3‘-dithiobis(succinimidylpropionate), and the resulting electrodes were further immobilized with Q-CdS using glutaraldehyde as a binding agent. The degree of anodic photocurrents was greatly influenced by charged conditions of hole scavengers used because of the presence of sulfonate groups on the Q-CdS surfaces; triethylamine having positive charges gave large photocurrents, triethanolamine medium photocurrents, and formate small photocurrents. If Q-CdS having a large emission from their surface trap states was used, anodic photocurrents were depressed with increasing anodic polarization from the onset potentials which were ca. −1.1 V vs SCE for the use of any kinds of hole scavengers, and the greatest depression appeared at −0.25 V, beyond which a steep increase in anodic photocurrents was seen. In contrast, no significant depression in photocurrents was observed and anodic photocurrents were monotonically increased, in the case of using Q-CdS having an intense band-gap emission. When the energetic position at the emission maximum is correlated to the potential at which the greatest photocurrent depression appeared, photocurrent−potential characteristics are discussed in terms of involvements of surface states in the photoelectrode reactions.