Photocatalytic reduction of cadmium and selenium ions and the deposition of cadmium selenide

摘要

Titanium dioxide (TiO2) photocatalysis, which can oxidise or reduce organic and inorganic pollutants, is a developing technology for water and wastewater treatment. The current work investigates the photocatalytic reduction of cadmium and selenium species as the presence of these elements in water are of environmental concern. Although TiO2 has been widely used for the photocatalytic process, its light absorption is limited to the UV region of the solar spectrum. Hence, the current project also explores the possibility to deposit cadmium selenide (CdSe) onto TiO2 to extend the photoresponse to the visible region. This study demonstrated that cadmium (Cd(II)) could be reduced to its metallic form by photocatalysis. The choice of hole scavengers and reaction pH are of importance in determining whether the photocatalytic reduction reaction will occur. It is also essential that both Cd(II) and organic additives are adsorbed on the surface of TiO2. A mechanism for cadmium photoreduction in the presence of formate as the hole scavenger was proposed. The current investigation elucidated the mechanism for the photoreduction of selenite (Se(IV)). Selenite was found to be photoreduced to its elemental form (Se(0)) as films, by direct photoreduction of Se(IV), and as discrete particles, by the reaction between Se(IV) and selenide (Se(2-)) ions. The Se(2-) ions are believed to have been generated from the 6 electron photoreduction of Se(IV) and/or the further photoreduction of the Se(0) deposits. Photocatalytic reduction reactions of Se(IV) and selenate (Se(VI)) using different commercial TiO2 materials was also studied. The current work also successfully deposited CdSe by photocatalysis using Se-TiO2 obtained from the photoreduction of Se(IV) and Se(VI). The mechanism for CdSe deposition was clarified and attributed to the reaction of Cd(II) present in the system and the Se(2-) released from the reduction of Se(0) upon further illumination. The Se¬TiO2 photocatalysts obtained from the photoreduction of different selenium precursors (Se(IV) and Se(VI)) resulted in the dominance of different morphologies of the CdSe particles. This suggests a new approach to manipulate the properties of CdSe during its formation, and hence control over electrical and optical properties of this semiconductor.