Abstract
Formation of iodine from air-saturated KI solution under natural sunlight (950±25 W m −2) with nanocrystals of TiO 2 in different phase compositions, ZnO and SnO 2, characterized by powder XRD, UV-visible diffuse reflectance and impedance spectroscopies, increases by 3–9 fold on impressing a cathodic bias of −0.2 V (vs NHE) to the semiconductors. The iodine generation essentially requires light, the semiconductor and dissolved oxygen. An anodic bias of +0.2 V (vs NHE) to the illuminated semiconductors fails to oxidize iodide ion from air-saturated KI solution. Under cathodic bias, mixtures of ZnO–TiO 2 rutile, SnO 2–TiO 2 rutile and ZnO–SnO 2 nanocrystals show higher photocatalytic activity, pointing to an improved charge separation in the oxide mixtures. The mechanism and the energetics of photocatalysis under cathodic bias are discussed. Also, the photocatalytic activities of the semiconductor nanocrystals are analyzed in terms of their optical, electrical and crystal properties.
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