Heterogeneous photocatalytic degradation of reactive dyes in aqueous TiO(2) suspensions: Decolorization kinetics

This work assesses the photocatalytic (TiO(2)/UV) degradation of a simulated reactive dye bath (Black 5, Red 239, Yellow 17, and auxiliary chemicals). Color removal was monitored by spectrophotometry. Mineralization was determined by DOC analyses. Photocatalytic, photolytic, and adsorption experiments were performed, showing that adsorption was negligible. After 30 min of irradiation, it was achieved 97% and 40% of color removal with photocatalysis and photolysis, respectively. No mineralization occurred within 30 min. A kinetic model composed of two, first-order in-series reactions was used. The first photocatalytic decolorization rate constant was k(1) = 2.6 min(-1) and the second k(2) = 0.011 min(-1). The fast decolorization of Reactive Black 5 dye is an indication that the number of azo and vinylsulfone groups in the dye molecule maybe a determining factor for the increased photolytic and photocatalytic color removal and degradation rates. (C) 2008 Elsevier B.V. All rights reserved.

Heterogeneous photocatalytic treatment of organic dyes in air and aqueous media

This review focuses on the heterogeneous photocatalytic treatment of organic dyes in air and water. Representative studies spanning approximately three decades are included in this review. These studies have mostly used titanium dioxide (TiO2) as the inorganic semiconductor photocatalyst of choice for decolorizing and decomposing the organic dye to mineralized products. Other semiconductors such as ZnO, CdS, WO3, and Fe2O3 have also been used, albeit to a much smaller extent. The topics covered include historical aspects, dark adsorption of the dye on the semiconductor surface and its role in the subsequent photoreaction, semiconductor preparation details, photoreactor configurations, photooxidation kinetics/mechanisms and comparison with other Advanced Oxidation Processes (e.g., UV/H2O2, ozonation, UV/O3, Fenton and photo-Fenton reactions), visible light-induced dye decomposition by sensitization mechanism, reaction intermediates and toxicity issues, and real-world process scenarios. © 2008 Elsevier B.V. All rights reserved.

TiO2/CuO films obtained by citrate precursor method for photocatalytic application

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

Photocatalytic hydrogen production by water splitting over Au-TiO2 commercial and home-made photocatalysts

[ES]Póster presentado en 3rd European Conference on Environmental Applications of Advanced Oxidation Processes.

El contenido del póster corresponde a parte del trabajo de tesis doctoral de la Dra. Cristina Rodríguez López.

Selective photo-oxidation of cellobiose with tio2-supported metal nanoparticles

Upgrade of biomass to valuable chemicals is a central topic in modern research due to the high availability and low price of this feedstock. For the difficulties in biomass treatment, different pathways are still under investigation. A promising way is in the photodegradation, because it can lead to greener transformation processes with the use of solar light as a renewable resource. The aim of my work was the research of a photocatalyst for the hydrolysis of cellobiose under visible irradiation. Cellobiose was selected because it is a model molecule for biomass depolymerisation studies. Different titania crystalline structures were studied to find the most active phase. Furthermore, to enhance the absorption of this semiconductor in the visible range, noble metal nanoparticles were immobilized on titania. Gold and silver were chosen because they present a Surface Plasmon Resonance band and they are active metals in several photocatalytic reactions. The immobilized catalysts were synthesized following different methods to optimize the synthetic steps and to achieve better performances. For the same purpose the alloying effect between gold and silver nanoparticles was examined.

Selective photo-oxidation of glucose

Biomass transformation into high-value chemicals has attracted attention according to the “green chemistry” principles. Low price and high availability make biomass one of the most interesting renewable resources as it provides the means to create sustainable alternatives to the oil-derived building blocks of the chemical industry In recent year, the need for alternative environmentally friendly routes to drive chemical reactions has in photocatalytic processes an interesting way to obtain valuable chemicals from various sources using the solar light as energy source. The purpose of this work was to use supported noble metal nanoparticles in the selective photo-oxidation of glucose through using visible light. Glucose was chosen as model molecule because it is the cheapest and the most common monosaccharide. Few studies about glucose photo oxidation have been conducted so far, and reaction mechanism is still not totally explained. The aim of this work was to systematically analyze and assess the impact of several parameters (eg. catalyst/substrate ratio, reaction time, effect of the solvent and light source) on the reaction pathway and to monitor the product distribution in order to draw a general reaction scheme for the photo oxidation of glucose under visible light. This study regards the reaction mechanism and the influence of several parameters, such as solvent, light power and substrate concentration. Furthermore, the work focuses on the influence of gold and silver nanoparticles and on the influence of metal loading. The glucose oxidation was monitored through the mass balance and the products selectivity. Reactions were evaluated in terms of glucose conversion, mass balance and selectivities towards arabinose and gluconic acid. In conclusion, this study is able to demonstrate that the photo oxidation of glucose under visible light is feasible; the full identification of the main products allows, for the first time, a comprehensive reaction mechanism scheme.

Fe-doped and -mediated graphitic carbon nitride nanosheets for enhanced photocatalytic performance under natural sunlight

Herein, we demonstrate the synthesis of highly efficient Fe-doped graphitic carbon nitride (g-C3N4) nanosheets via a facile and cost effective method. The synthesized Fe-doped g-C3N4 nanosheets were well characterized by various analytical techniques. The results revealed that the Fe exists mainly in the +3 oxidation state in the Fe-doped g-C3N4 nanosheets. Fe doping of g-C3N4 nanosheets has a great influence on the electronic and optical properties. The diffuse reflectance spectra of Fe-doped g-C3N4 nanosheets exhibit red shift and increased absorption in the visible light range, which is highly beneficial for absorbing the visible light in the solar spectrum. More significantly, the Fe-doped g-C3N4 nanosheets exhibit greatly enhanced photocatalytic activity for the degradation of Rhodamine B under sunlight irradiation. The photocatalytic activity of 2 mol% Fe-doped g-C3N4 nanosheets is almost 7 times higher than that of bulk g-C3N4 and 4.5 times higher than that of pure g-C3N4 nanosheets. A proposed mechanism for the enhanced photocatalytic activity of Fe-doped g-C3N4 nanosheets was investigated by trapping experiments. The synthesized photocatalysts are highly stable even after five successive experimental runs. The enhanced photocatalytic performance of Fe-doped g-C3N4 nanosheets is due to high visible light response, large surface area, high charge separation and charge transfer. Therefore, the Fe-doped g-C3N4 photocatalyst is a promising candidate for energy conversion and environmental remediation.

Photocatalytic Concretes – The interface between photocatalysis and cement chemistry

We thank the European Commission for financial support through the European Project Light2CAT, funded by the European Union’s Seventh Framework Programme (FP7) under the grant agreement no. 283062 Eco-Innovation, Theme Environment

Photocatalytic activities of tin(IV) oxide surface-modified titanium(IV) dioxide show a strong sensitivity to the TiO 2 crystal form

Surface modification of rutile TiO2 with extremely small SnO2 clusters gives rise to a great increase in its UV light activity for degradation of model organic water pollutants, while the effect is much smaller for anatase TiO2. This crystal form sensitivity is rationalized in terms of the difference in the electronic modification of TiO2 through the interfacial Sn−O−Ti bonds. The increase in the density of states near the conduction band minimum of rutile by hybridization with the SnO2 cluster levels intensifies the light absorption, but this is not seen with modified anatase. The electronic transition from the valence band to the conduction band causes the bulk-to-surface interfacial electron transfer to enhance charge separation. Further, electrons relaxed to the conduction minimum are smoothly transferred to O2 due to the action of the SnO2 species as an electron transfer promoter.

Lead oxide-modified TiO2 photocatalyst: tuning light absorption and charge carrier separation by lead oxidation state

Modification of TiO2 with metal oxide nanoclusters such as FeOx, NiOx has been shown to be a promising approach to the design of new photocatalysts with visible light absorption and improved electron–hole separation. To study further the factors that determine the photocatalytic properties of structures of this type, we present in this paper a first principles density functional theory (DFT) investigation of TiO2 rutile(110) and anatase(001) modified with PbO and PbO2 nanoclusters, with Pb2+ and Pb4+ oxidation states. This allows us to unravel the effect of the Pb oxidation state on the photocatalytic properties of PbOx-modified TiO2. The nanoclusters adsorb strongly at all TiO2 surfaces, creating new Pb–O and Ti–O interfacial bonds. Modification with PbO and PbO2 nanoclusters introduces new states in the original band gap of rutile and anatase. However the oxidation state of Pb has a dramatic impact on the nature of the modifications of the band edges of TiO2 and on the electron–hole separation mechanism. PbO nanocluster modification leads to an upwards shift of the valence band which reduces the band gap and upon photoexcitation results in hole localisation on the PbO nanocluster and electron localisation on the surface. By contrast, for PbO2 nanocluster modification the hole will be localised on the TiO2 surface and the electron on the nanocluster, thus giving rise to two different band gap reduction and electron–hole separation mechanisms. We find no crystal structure sensitivity, with both rutile and anatase surfaces showing similar properties upon modification with PbOx. In summary the photocatalytic properties of heterostructures of TiO2 with oxide nanoclusters can be tuned by oxidation state of the modifying metal oxide, with the possibility of a reduced band gap causing visible light activation and a reduction in charge carrier recombination.

Correlation between the photocatalysed oxidation of methylene blue in solution and the reduction of resazurin in a photocatalyst activity indicator ink (Rz Paii)

Pathways of the Photocatalytic Reaction of Acetate in H2O and D2O Combined: An EPR and ATR-FTIR Study

The adsorption and photocatalytic degradation of acetate on TiO2 surfaces was investigated in H2O and D2O by ATR-FTIR and EPR Spectroscopy respectively. These studies were carried out in the dark and under UV(A) illumination to gain additional insights into the adsorption behaviour with the identification of paramagnetic species formed during the oxidation of acetate. Isotopic exchange during the adsorption of D2O on TiO2 surface led to different interactions between the adsorbate and OD groups. At different pH levels, several surface complexes of acetate can be formed such as monodentate, or bidentates. Under UV(A) irradiation of TiO2 aqueous suspensions, the formation of hydroxyl and methoxy radicals evidenced as the corresponding spin-adducts, were found to dominate in alkaline and acidic suspensions respectively. Two possible pathways for the oxidation of acetate have been suggested at different pH levels in solution in terms of the source of the spin adduct formed. These proposed pathways were found to be in good agreement with ATR-FTIR and EPR results.

Titanium dioxide based nanomaterials for photocatalytic water treatment

Water treatment using photocatalysis has gained extensive attention in recent years. Photocatalysis is promising technology from green chemistry point of view. The most widely studied and used photocatalyst for decomposition of pollutants in water under ultraviolet irradiation is TiO2 because it is not toxic, relatively cheap and highly active in various reactions. Within this thesis unmodified and modified TiO2 materials (powders and thin films) were prepared. Physico-chemical properties of photocatalytic materials were characterized with UV-visible spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectrometry (XPS), inductively coupled plasma optical emission spectroscopy (ICP-OES), ellipsometry, time-of-flight secondary ion mass spectrometry (ToF-SIMS), Raman spectroscopy, goniometry, diffuse reflectance measurements, thermogravimetric analysis (TGA) and nitrogen adsorption/desorption. Photocatalytic activity of prepared samples in aqueous environment was tested using model compounds such as phenol, formic acid and metazachlor. Also purification of real pulp and paper wastewater effluent was studied. Concentration of chosen pollutants was measured with high pressure liquid chromatography (HPLC). Mineralization and oxidation of organic contaminants were monitored with total organic carbon (TOC) and chemical oxygen demand (COD) analysis. Titanium dioxide powders prepared via sol-gel method and doped with dysprosium and praseodymium were photocatalytically active for decomposition of metazachlor. The highest degradation rate of metazachlor was observed when Pr-TiO2 treated at 450ºC (8h) was used. The photocatalytic LED-based treatment of wastewater effluent from plywood mill using commercially available TiO2 was demonstrated to be promising post-treatment method (72% of COD and 60% of TOC was decreased after 60 min of irradiation). The TiO2 coatings prepared by atomic layer deposition technique on aluminium foam were photocatalytically active for degradation of formic and phenol, however suppression of activity was observed. Photocatalytic activity of TiO2/SiO2 films doped with gold bipyramid-like nanoparticles was about two times higher than reference, which was not the case when gold nanospheres were used.

Effect of cold plasma pre-treatment on photocatalytic activity of 3D fabric loaded with nano-photocatalysts: response surface methodology

In this study, the physico-chemical effects occasioned by the cold plasma discharge (CPD) on the photo-decolorization of Reactive Orange 16 (RO16) by 3D fabrics (spacer fabrics) loaded with ZnO:TiO2 nano-photocatalysts (nphs) were optimized via response surface methodology (RSM). CPD was employed to improve the surface characteristics of the spacer fabrics for nphs loading. Surface morphology and color variation were studied utilizing scanning electron microscopy (SEM) and CIE-Lab system, respectively. The effect of CPD on the wetting ability of the spacer fabrics was examined using dynamic adsorption measurement (DAM). Also, X-ray fluorescence (XRF) was utilized to investigate the durability of the nphs on the spacer fabrics. All the experiments were implemented in a Box-Behnken design (BBD) with three independent variables (CPD treatment time, dye concentration and irradiation time) in order to optimize the decolorization of RO16. The anticipated values of the decolorization efficiency were found to be in excellent agreement with the experimental values (R2 = 0.9996, Adjusted R2 = 0.9992). The kinetic analysis demonstrated that the photocatalytic decolorization followed the Langmuir-Hinshelwood kinetic model. In conclusion, this heterogeneous photocatalytic process is capable of decolorizing and mineralizing azoic reactive dye in textile wastewater. Moreover, the results confirmed that RSM based on the BBD was a suitable method to optimize the operating conditions of RO16 degradation.