Photocatalytic decomposition of rhodamine-B using scandium and silver-modified TiO2 Powders

Semiconductor-mediated photocatalytic oxidation is an interesting method for water decontamination and a specially modified TiO2 is said to be a promising material. This study verified that the synthesis of 1wt%Ag modified-Sc0.01Ti0.99O1.995 powder samples prepared by Polymeric Precursor Method is capable of forming a mixture of anatase-rutile phase with high photocatalytic performance. This kind of material is found to have a lower bandgap compared to the TiO2-anatase commercial powders, which can be associated to an innovative hybrid modification. The simultaneous insertion of scandium in order to generate a p-type semiconductor and a metallic silver nanophase acting as an electron trapper demonstrated being capable of enhancing the degradation of rhodamine B compared to the commercial TiO2. In spite of the different thermal treatments or phase amounts, the hybrid modified powder samples showed higher photocatalytic activity than the commercial ones.

Role of Platinum Deposited on TiO2 in Photocatalytic Methanol Oxidation and Dehydrogenation Reactions

Titania modified nanoparticles have been prepared by the photodeposition method employing platinum particles on the commercially available titanium dioxide (Hombikat UV 100). The properties of the prepared photocatalysts were investigated by means of the Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), atomic force microscopy (AFM), and UV-visible diffuse spectrophotometry (UV-Vis). XRD was employed to determine the crystallographic phase and particle size of both bare and platinised titanium dioxide. The results indicated that the particle size was decreased with the increasing of platinum loading. AFM analysis showed that one particle consists of about 9 to 11 crystals. UV-vis absorbance analysis showed that the absorption edge shifted to longer wavelength for 0.5% Pt loading compared with bare titanium dioxide. The photocatalytic activity of pure and Pt-loaded TiO2 was investigated employing the photocatalytic oxidation and dehydrogenation of methanol. The results of the photocatalytic activity indicate that the platinized titanium dioxide samples are always more active than the corresponding bare TiO2 for both methanol oxidation and dehydrogenation processes. The loading with various platinum amounts resulted in a significant improvement of the photocatalytic activity of TiO2. This beneficial effect was attributed to an increased separation of the photogenerated electron-hole charge carriers.

Dye-sensitized solar cells based on perylene derivatives

The oil price rises more and more, and the world energy consumption is projected to expand by 50 percent from 2005 to 2030. Nowadays intensive research is focused on the development of alternative energies. Among them, there are dye-sensitized nanocrystalline solar cells (DSSCs) “the third generation solar cells”. The latter have gained attention during the last decade and are currently subject of intense research in the framework of renewable energies as a low-cost photovoltaic. At present DSSCs with ruthenium based dyes exhibit highest efficiencies (ca 11%). The objective of the present work is to fabricate, characterize and improve the performance of DSSCs based on metal free dyes as sensitizers, especially on perylene derivatives. The work begins by a general introduction to the photovoltaics and dye-sensitized solar cells, such as the operating principles and the characteristics of the DSSCs. Chapter 2 and 3 discuss the state of the art of sensitizers used in DSSCs, present the compounds used as sensitizer in the present work and illustrate practical issues of experimental techniques and device preparation. A comparative study of electrolyte-DSSCs based on P1, P4, P7, P8, P9, and P10 are presented in chapter 4. Experimental results show that the dye structure plays a crucial role in the performance of the devices. The dye based on the spiro-concept (bipolar spiro compound) exhibited a higher efficiency than the non-spiro compounds. The presence of tert-butylpyridine as additive in the electrolyte was found to increase the open circuit voltage and simultaneously decrease the efficiency. The presence of lithium ions in the electrolyte increases both output current and the efficiency. The sensitivity of the dye to cations contained in the electrolyte was investigated in the chapter 5. FT-IR and UV-Vis were used to investigate the in-situ coordination of the cation to the adsorbed dye in the working devices. The open-circuit voltage was found to depend on the number of coordination sites in the dye. P1 with most coordination sites has shown the lowest potential drop, opposite to P7, which is less sensitive to cations in the working cells. A strategy to improve the dye adsorption onto the TiO2 surface, and thus the light harvesting efficiency of the photoanode by UV treatment, is presented in chapter 6. The treatment of the TiO2 film with UV light generates hydroxyl groups and renders the TiO2 surface more and more hydrophilic. The treated TiO2 surface reacts readily with the acid anhydride group of the dye that acts as an anchoring group and improves the dye adsorption. The short-circuit current density and the efficiency of the electrolyte-based dye cells was considerably improved by the UV treatment of the TiO2 film. Solid-state dye-sensitized solar cells (SSDs) based on spiro-MeOTAD (used as hole transport material) are studied in chapter 7. The efficiency of SSDs was globally found to be lower than that of electrolyte-based solar cells. That was due to poor pore filling of the dye-loaded TiO2 film by the spin-coated spiro-MeOTAD and to the significantly slower charge transport in the spiro-MeOTAD compared to the electrolyte redox mediator. However, the presence of the donor moieties in P1 that are structurally similar to spiro-MeOTAD was found to improve the wettability of the P1-loaded TiO2 film. As a consequence the performance of the P1-based solid-state cells is better compared to the cells based on non-spiro compounds.

Interlamellar modification of smectite clays

Clay minerals, both natural and synthetic, have a wide range of applications. Smectite clays are not true insulators, their slight conductivity has been utilized by the paper industry in the development of mildly conducting paper. In particular, the synthetic hectorite clay, laponite, is employed to produce paper which is used in automated drawing offices where electro graphic printing is common. The primary objective of this thesis was to modify smectite clays, particularly laponite, to achieve enhanced conductivity. The primary objective was more readily achieved if the subsidiary objective of understanding the mechanism of conductivity was defined. The cyclic voltammograms of some cobalt complexes were studied in free solution and as clay modified electrodes to investigate the origin of electroactivity in clay modified electrodes. The electroactivity of clay modified electrodes prepared using our method can be attributed to ion pairs sorbed to the surface of the electrode, in excess of the cationic exchange capacity. However, some new observations were made concerning the co-ordination chemistry of the tri-2-pyridylamine complexes used which needed clarification. The a.c. conductivity of pressed discs of laponite RD was studied over the frequency range 12Hz- 100kHz using three electrode systems namely silver-loaded epoxy resin (paste), stainless-steel and aluminium. The a. c. conductivity of laponite consists of two components, reactive (minor) and ionic (major) which can be observed almost independently by utilizing the different electrode systems. When the temperature is increased the conductivity of laponite increases and the activation energy for conductivity can be calculated. Measurement of the conductivity of thin films of laponite RD in two crystal planes shows a degree of anisotropy in the a.c. conductivity. Powder X-ray diffraction and 119Sn Mossbauer spectroscopy studies have shown that attempts to intercalate some phenyltin compounds into laponite RD under ambient conditions result in the formation of tin(IV) oxide pillars. 119Sn Mossbauer data indicate that the order of effectiveness of conversion to pillars is in the order: Ph3SnCl > (Ph3Sn)2O, Ph2SnCl2 The organic product of the pillaring process was identified by 13C m.a.s.n.m.r. spectroscopy as trapped in the pillared lattice. This pillaring reaction is much more rapid when carried out in Teflon containers in a simple domestic microwave oven. These pillared clays are novel materials since the pillaring is achieved via neutral precursors rather than sacrificial reaction of the exchangeable cation. The pillaring reaction depends on electrophilic attack on the aryl tin bond by Brønsted acid sites within the clay. Two methods of interlamellar modification were identified which lead to enhanced conductivity of laponite, namely ion exchange and tin(IV) oxide pillaring. A monoionic potassium exchanged laponite shows a four fold increase in a.c. conductivity compared to sodium exchanged laponite RD. The increased conductivity is due to the appearence of an ionic component. The conductivity is independent of relative humidity and increases with temperature. Tin(IV) oxide pillared laponite RD samples show a significant increase in conductivity. Samples prepared from Ph2SnCl2 show an increase in excess of an order of magnitude. The conductivity of tin(IV) oxide pillared laponite samples is dominated by an ionic component.

Silver ion release from electrodes of nanotubes of TiO2 impregnated with Ag nanoparticles applied in photoelectrocatalytic disinfection

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Light harvesting in solar cells using natural pigments from red fruits adsorbed to mesoporous TiO2

Nature has developed strategies to present us with a wide variety of colours, from the green of leaves to the bright colours seen in flowers. Anthocyanins are between these natural pigments that are responsible for the great diversity of colours seen in flowers and fruits. Anthocyanins have been used to sensitize titanium dioxide (TiO2) in Dye-Sensitized Solar Cells (DSSCs). DSSCs have become one of the most popular research topic in photovoltaic cells due to their low production costs when compared to other alternatives. DSSCs are inspired in what happens in nature during photosynthesis. A primary charge separation is achieved by means of a photoexcited dye capable of performing the electron injection into the conduction band of a wide band-gap semiconductor, usually TiO2. With this work we aimed to synthesize a novel mesoporous TiO2 structure as the semiconductor in order to increase the dye loading. We used natural occurring dyes such as anthocyanins and their synthetic flavylium relatives, as an alternative to the widely used metal complexes of Ru(II) which are expensive and are environmentally unsafe. This offers not only the chance to use safer dyes for DSSCs, but also to take profit of waste biological products, such as wine and olive oil production residues that are heavily loaded with anthocyanin dyes. We also performed a photodegradation study using TiO2 as the catalyst to degrade dye contaminants, such as those from the wine production waste, by photo-irradiation of the system in the visible region of the light spectrum. We were able to succeed in the synthesis of mesoporous TiO2 both powder and thin film, with a high capacity to load a large amount of dye. We proved the concept of photodegradation using TiO2 as catalyst. And finally, we show that wine production waste is a possible dye source to DSSCs application.

Thin films composed of Ag nanoclusters dispersed in TiO2: Influence of composition and thermal annealing on the microstructure and physical responses

Noble metal powders containing gold and silver have been used for many centuries, providing different colours in the windows of the medieval cathedrals and in ancient Roman glasses. Nowadays, the interest in nanocomposite materials containing noble nanoparticles embedded in dielectric matrices is related with their potential use for a wide range of advanced technological applications. They have been proposed for environmental and biological sensing, tailoring colour of functional coatings, or for surface enhanced Raman spectroscopy. Most of these applications rely on the so-called localised surface plasmon resonance absorption, which is governed by the type of the noble metal nanoparticles, their distribution, size and shape and as well as of the dielectric characteristics of the host matrix. The aim of this work is to study the influence of the composition and thermal annealing on the morphological and structural changes of thin films composed of Ag metal clusters embedded in a dielectric TiO2 matrix. Since changes in size, shape and distribution of the clusters are fundamental parameters for tailoring the properties of plasmonic materials, a set of films with different Ag concentrations was prepared. The optical properties and the thermal behaviour of the films were correlated with the structural and morphological changes promoted by annealing. The films were deposited by DC magnetron sputtering and in order to promote the clustering of the Ag nanoparticles the as-deposited samples were subjected to an in-air annealing protocol. It was demonstrated that the clustering of metallic Ag affects the optical response spectrum and the thermal behaviour of the films.

Síntese, caracterização e atividade fotocatalítica de catalisadores nanoestruturados de TiO2 dopados com metais

Titanium dioxide nanostructured catalysts (nanotubes) doped with different metals (silver, gold, copper, palladium and zinc) were synthesized by the hydrothermal method in order to promote an increase in their photocatalytic activity under visible light. The catalysts were characterized by X-ray diffraction, diffuse reflectance spectroscopy, transmission electron microscopy and specific area and pore volume determination. The materials' photocatalytic activity was evaluated by rhodamine B decomposition in a glass batch reactor. Under UV radiation, only nanotubes doped with palladium were more active than the TiO2 P25, but the samples doped with silver, palladium and gold exhibited better results than the undoped samples under visible light.

Preparation and characterization of nanocrystalline transition metal-loaded sulfated titania through sol-gel method

Transition metal-loaded (3%) nanocrystalline sulfated titania (ST) powders are prepared using the sol–gel technique. Anatase is found as the active phase in all the samples. Sulfate ion impregnation decreases the crystallite size and stabilizes the anatase phase of TiO2. Acidity of the samples is found to increase by the incorporation of sulfate ion and also by the modification by transition metal ions. All the prepared catalysts are found stable up to 700 °C.

Gas phase photocatalytic bacteria inactivation using metal modified TiO2 catalysts

The present study describes the efficiency of heterogeneous photocatalytic reactor for the inactivation of three air born bacteria, Escherichia coli, Bacillus subtilis and Staphylococcus aureus using metal modified TiO2 photocatalysts and blacklight irradiation. The catalysts were prepared by photodeposition of silver, palladium or iron on commercial TiO2, immobilized on glass plates. X-ray photoelectron spectroscopy analysis was applied to determine the atomic percentage and species of each metal on the TiO2 surface, showing that 85% of silver, 73% of palladium and 45% of iron were present in metallic form on TiO2 surface. The plates were positioned on the inner lateral walls of a chamber through which the contaminated air flow passed for disinfection. Irradiation of bare TiO 2 resulted in 50% inactivation of E. coli while 41% and 35% inactivation of B. subtilis and S. aureus were obtained, respectively. When metal modified TiO2 was applied, the inactivation of B. subtilis was improved to 91% using Pd-TiO2 while of S. aureus was improved to 94% with Fe-TiO2, showing in this case no significant difference when compared to Ag-TiO2 and Pd-TiO2. In contrast, inactivation of E. coli was not significantly increased when metal modified TiO2 was used, ranging from 47% to 57%. © 2012 Elsevier B.V.

Fotocatálise heterogênea em instrumental odontológico recoberto com nanopartículas TiO2 e Ag

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Avaliação da ação bactericida e bacteriostática das nanopartículas TiO2 e Ag aplicadas em pinos intraradiculares

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Degradação de poluentes orgânicos utilizando filmes de TiO2 modificados com íons prata

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Fotocatálise heterogênea de enterococcus faecalis e pseudomonas aeruginosa desencadeada pela ação da luz UV e branca em espátulas com revestimento de nanopartículas TiO2 e Ag

Nanotechnology, the science of minuscule, has developed products which are able t o manipulate atoms and molecules that could be applied in the sterilization process of dental instruments. Objetives: The objective of the present study was to evaluate the self-cleaning action of TiO2 and Ag nanoparticles coating on dental instruments by the photocataliys process under UV and visible light irradiation. Material and method: Microbiologic tests were done using dental cement spatulas coated with TiO2 and Ag nanoparticles (one or three layers), and contaminated with 10 mcrl of Pseudomonas aeruginosa and Enterococcus faecalis, respectively. After contamination, they were exposed to ultraviolet light and visible light for 120 minutes. Next, they were transferred to and stored in test tubes with BHI (Brain Heart Infusion) and incubated in 35 to 37 °C. Checking times for bacterial growth and for control and retrieval tests were done at: 24, 48, 72 and 96 hours. Result: The Pseudomonas aeruginosa was inactive after 120 minutes of ultraviolet light irradiation, thus confirming the heterogeneous photocatalytic activity of TiO2 and Ag. The Pseudomonas aeruginosa was not inactivated under visible light irradiation and the Enterococcus faecalis was not inactivated under UV and visible light irradiation of the dental cement spatulas coated with TiO2 and Ag nanoparticles in the readings to 96 hours, showing bacterial growth. Conclusion: There were no influence of one or three layers of TiO2 and Ag nanoparticles coating of the spatulas in the results. The heterogeneous photocatalysis activity of TiO2 and Ag under UV light irradiation was confirmed for Pseudomonas aeruginosa but not under visible light. Enterococcus faecalis did not confirmed the photocatalytics activity of TiO2 and Ag under UV light irradiation and visible lights irradiation.

Photocatalytic decomposition of rhodamine-b using scandium and silver-modified TiO2 powders

Semiconductor-mediated photocatalytic oxidation is an interesting method for water decontamination and a specially modified TiO2 is said to be a promising material. This study verified that the synthesis of 1wt%Ag modified-Sc0.01Ti0.99O1.995 powder samples prepared by Polymeric Precursor Method is capable of forming a mixture of anatase-rutile phase with high photocatalytic performance. This kind of material is found to have a lower bandgap compared to the TiO2-anatase commercial powders, which can be associated to an innovative hybrid modification. The simultaneous insertion of scandium in order to generate a p-type semiconductor and a metallic silver nanophase acting as an electron trapper demonstrated being capable of enhancing the degradation of rhodamine B compared to the commercial TiO2. In spite of the different thermal treatments or phase amounts, the hybrid modified powder samples showed higher photocatalytic activity than the commercial ones.