Synthesis and characterization of ZrO2–TiO2 binary oxide semiconductor nanoparticles: Application and interparticle electron transfer process
A series of nanocrystalline mesoporous ZrO2–TiO2 binary oxide photocatalysts with different wt% of ZrO2 and TiO2 were prepared by a sol–gel method. These binary oxide photocatalysts were characterized by XRD, N2 adsorption–desorption, DRS, FTIR, Raman spectroscopy, photoluminescence and TEM analyses. Detailed investigations revealed that the ZrO2–TiO2 catalysts are highly micro-crystalline in nature with a larger surface area than that of the pure TiO2 or ZrO2 catalysts since the added ZrO2 plays an important role in promoting the formation of nanoparticles with an anatase structure, high surface area and acidity. The photocatalytic reactivity of the catalysts was investigated for the degradation of 4-chlorophenol in an aqueous phase in which the ZrO2–TiO2 photocatalysts were found to exhibit remarkably higher photocatalytic reactivity than that of pure TiO2 and ZrO2. The catalytic activity of the binary oxide photocatalysts for the degradation of 4-chlorophenol was observed to be gradually enhanced with an increase in the ZrO2 content and reached an optimum at 12 wt% of ZrO2 while maintaining the same percentage degradation with further loading of ZrO2 until 50 wt%. Such high reactivity is due to the easy transfer of the photo-formed electrons from the conduction band surface trap states of ZrO2 to the conduction band of TiO2 through strong chemical interactions, thereby, preventing the radiative recombination of the photo-formed electrons and holes. The ZrO2–TiO2 catalysts were, thus, found to be highly active for the efficient degradation of 4-chlorophenol and, in fact, exhibited just as efficient activity as the commercial P-25, Degussa TiO2 catalysts, and a new reaction mechanism has, hereby, been proposed.
Graphical abstractThe chemical interaction of Zr–O–Ti in the binary oxide catalysts is found to be a major factor in high performance for the degradation of 4-CP. Photoluminescence provides strong evidence for the existence of the ZrO2 CB surface trap states which lie below the CB of TiO2 and facilitate fast electrons injection to the CB of TiO2 and which prevent the recombination of electrons and holes.Figure optionsDownload full-size imageDownload as PowerPoint slide
Journal: Applied Catalysis A: General - Volume 333, Issue 2, 15 December 2007, Pages 264–271