Visible Light Reductive Photocatalysis of Azo-Dyes with n-n Junctions Based on Chemically Deposited CdS

New composite photocatalysts have been obtained by chemical bath deposition of CdS on top of either nanostructured crystalline ZrO₂ or TiO₂ films previously deposited on conductive glass FTO. Their morphological, photoelectrochemical and photochemical properties have been investigated and compared. Time resolved spectroscopic, techniques show that in FTO/TiO₂/CdS films the radiative recombination of charges, separated by visible illumination of CdS, is faster than in FTO/ZrO₂/CdS, evidencing that carrier dynamics in the two systems is different. Photoelectrochemical investigation evidence a suppression of electron collection in ZrO₂/CdS network, whereas electron injection from CdS to TiO₂ is very efficient since trap states of TiO₂ act as a reservoir for long lived electrons storage. This ability of FTO/TiO₂/CdS films is used in the reductive cleavage of N=N bonds of some azo-dyes by visible light irradiation, with formation and accumulation of reduced aminic intermediates, identified by ESI-MS analysis. Needed protons are provided by sodium formate, a good hole scavenger that leaves no residue upon oxidation. FTO/TiO₂/CdS has an approximately 100 meV driving force larger than FTO/ZrO₂/CdS under illumination for azo-dye reduction and it is always about 10% more active than the seconds. The films showed very high stability and recyclability, ease of handling and recovering.