Virtually Transparent TiO2/Polyelectrolyte Thin Multilayer Films as High-Efficiency Nanoporous Photocatalytic Coatings for Breaking Down Formic Acid and for Escherichia coli Removal.

Virtually transparent photocatalytic multilayer films composed of TiO2 nanoparticles and polyelectrolytes were built on model surfaces using layer-by-layer assembly and investigated as photocatalytic nanoporous coatings. Formic acid (HCOOH) and Escherichia coli were used as models for the degradation of gaseous pollutants and for studying antibacterial properties. Positively charged TiO2 nanoparticles were coassembled with negatively charged poly(sodium 4-styrenesulfonate) (NaPSS) which leads to highly transparent nanoscale coatings in which the content of TiO2 particles is controlled mainly by the number of deposition cycles and the enhanced translucency with respect to titania powders is likely due to the presence of the polyelectrolytes in the interstitial space between the particles. Build-up and structural properties of the films were determined by ellipsometry, quartz crystal microbalance (QCM-D, with dissipation monitoring), and UV-vis spectrophotometry in transmission and scanning electron microscopy. Complementary photophysical and activity tests of (PSS/TiO2)n multilayer films were performed in the gas-phase under UV-A light and revealed a peculiar dependence on the number of layer pairs (LPs), corresponding to a clear deviation from the usual observations in photocatalysis with increasing TiO2 amounts. Most notably, a single LP film showed a strongly enhanced HCOOH mineralization and outperformed films with a higher number of LPs, with respect to the quantity of TiO2 catalyst present in the films. It is believed that the high quantum yield (8.1%) of a coating consisting of a single TiO2 layer which is 6-7 times higher than that of a 6-10 LP film could be due to the optimum accessibility of the TiO2 crystallites toward both HCOOH and water molecules. In thicker films, while no detrimental light screening was observed with increasing the number of LPs, diffusion phenomena could cap the efficiency of the access of the pollutant and water to the catalytic surface. Unlike for HCOOH mineralization, three PSS/TiO2 LPs were required for observing a maximum antibacterial activity of the nanocomposite coatings. This is likely due to the fact that micrometer-sized E. coli bacteria do not enter into the interstitial space between the TiO2 particles and require a different surface morphology with respect to the number of active contact points for optimum degradation.

Heterojunction of CuO nanoclusters with TiO2 for photo-oxidation of organic compounds and for hydrogen production.

Heterojunctions of small CuO nanoclusters (synthesized by radiolysis) with TiO2 (commercial P25) induced a photocatalytic activity under visible light irradiation in a wide range of wavelengths due to the narrow bandgap of CuO nanoclusters of around 1.7 eV. The optical, chemical, and electrical properties of these composite nanomaterials were studied. The photocatalytic properties of bare and modified TiO2-P25 were studied for water purification (photooxidation of organic compounds such as phenol and 2-propanol) and for hydrogen generation under visible light irradiation. Time resolved microwave conductivity signals showed activation of TiO2 under visible light, proving the injection of electrons from CuO nanoclusters to the conduction band of TiO2-P25. The modified materials showed high photocatalytic activity under visible light. The important role of charge-carriers was demonstrated for both photoreduction and photooxidation reactions.

Inhibition of Fungal Growth Using Modified TiO2 with Core@Shell Structure of Ag@CuO Clusters.

The photocatalytic disinfection (PCD) properties of TiO2 have attracted attention in the research communities because the produced reactive oxygen species (ROS) allow destruction of different types of microbes, such as fungi, bacteria, viruses, algae, unicellular organisms, etc. on surfaces, in water, and in air. However, TiO2 requires UV irradiation to produce the ROS, which limits its photoactivity in indoor environments. Surface-modified TiO2 with small Ag and CuO nanoclusters in a core-shell structure exhibits antifungal properties under dark and visible conditions, possibly because of the interaction between Ag-CuO nanoclusters in the fungi membrane and their penetration, and the co-presence of Cu2+ and Ag+ ions. Therefore, a synergetic effect is obtained with co-modification of TiO2 with silver and copper, and the sample Ag@CuO/TiO2 (core-shell structure of Ag-Cu in a ratio of 1:3) exhibits the highest antifungal activity; that is, fungi growth inhibition is observed for Aspergillus melleus and Penicillium chrysogenum. Moreover, significant inhibitions of the sporulation and generation of droplets, possibly containing mycotoxins and sclerotia under dark and visible exposure, are also obtained.