TiO(2)-PHOTOCATALYZED DEGRADATION OF PHENOL IN SALINE MEDIA IN AN ANNULAR REACTOR: HYDRODYNAMICS, LUMPED KINETICS, INTERMEDIATES, AND ACUTE TOXICITY

The photocatalytic degradation of phenol in aqueous suspensions of TiO(2) under different salt concentrations in an annular reactor has been investigated. In all cases, complete removal of phenol and mineralization degrees above 90% were achieved. The reactor operational parameters were optimized and its hydrodynamics characterized in order to couple mass balance equations with kinetic ones. The photodegradation of the organics followed a Langmuir-Hinshelwood-Hougen- Watson lumped kinetics. From GC/MS analyses, several intermediates formed during oxidation have been identified. The main ones were catechol, hydroquinone, and 3-phenyl-2-propenal, in this order. The formation of negligible concentrations of 4-chlorophenol was observed only in high salinity medium. Acute toxicity was determined by using Artemia sp. as the test organism, which indicated that intermediate products were all less toxic than phenol and a significant abatement of the overall toxicity was accomplished, regardless of the salt concentration.

Degradation of organic dyes by P25-reduced graphene oxide: influence of inorganic salts and surfactants

Treatment of coloured effluent treatment is a major issue for the textile industry. In this study, catalyst P25-graphene was prepared and applied for degrading dye from an aqueous solution. Three types of dyes were selected to determine the feasibility of the catalyst for the dye degradation, including sulphonic, azoic, and fluorescent dyes. P25-graphene catalyst showed good ability to degrade all selected dyes. The influence of inorganic salts and surfactants on the photocatalytic degradation of rhodamine B using catalyst P25-graphene was also investigated. The degradation of rhodamine B was suppressed by the presence of NaCl, but the effect of Na2SO4 was negligible. The degradation of rhodamine B was significantly suppressed by all three types of surfactant, namely anionic, cationic and non-ionic surfactants. NMR technique was used to investigate the mechanisms associated with this suppression.

Degradation of sulfamethoxazole in water by solar photo-Fenton. Chemical and toxicological evaluation

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Influence of solvent on the morphology and photocatalytic properties of ZnS decorated CeO2 nanoparticles

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

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.

Durability of Ag-TiO(2) Photocatalysts Assessed for the Degradation of Dichloroacetic Acid

The stability of Ag-TiO(2) photocatalysts was examined for the photocatalytic degradation of dichloroacetic acid (DCA) as a function of the recycling times. The photocatalytic activity was investigated by measuring the rate of H(+) ions released during the photodegradation of DCA and confirmed by measuring the total organic carbon removal. The photodegradation reactions were studied at pH 3 and pH 10 for a series of Ag-TiO(2) photocatalysts as different with Ag loadings. All the Ag-TiO(2) and bare TiO(2) photocatalysts showed a decrease in photocatalytic activity on recycling for the DCA photodegradation reaction. The decrease in activity can be attributed to poisoning of active sites by Cl(-) anions formed during the photocatalytic DCA degradation. The photocatalytic activity was, however, easily recovered by a simple washing technique. The reversibility of the poisoning is taken as evidence to support the idea that the recycling of Ag-P25 TiO(2) photocatalysts does not have a permanent negative effect on their photocatalytic performance for the degradation of DCA. The choice of the preparation procedure for the Ag-TiO2 photocatalysts is shown to be of significant importance for the observed changes in the photocatalytic activity of the Ag-TiO2 particles. Copyright (C) 2008 Victor M. Menendez-Flores et al. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

Integrating efficient filtration and visible-light photocatalysis by loading Ag-doped zeolite Y particles on aluminia nanofiber membrane

Filtration membrane technology has already been employed to remove various organic effluents produced from the textile, paper, plastic, leather, food and mineral processing industries. To improve membrane efficiency and alleviate membrane fouling, an integrated approach is adopted that combines membrane filtration and photocatalysis technology. In this study, alumina nanofiber (AF) membranes with pore size of about 10 nm (determined by the liquid-liquid displacement method) have been synthesized through an in situ hydrothermal reaction, which permitted a large flux and achieved high selectivity. Silver nanoparticles (Ag NPs) are subsequently doped on the nanofibers of the membranes. Silver nanoparticles can strongly absorb visible light due to the surface plasmon resonance (SPR) effect, and thus induce photocatalytic degradation of organic dyes, including anionic, cationic and neutral dyes, under visible light irradiation. In this integrated system, the dyes are retained on the membrane surface, their concentration in the vicinity of the Ag NPs are high and thus can be efficiently decomposed. Meanwhile, the usual flux deterioration caused by the accumulation of the filtered dyes in the passage pores can be avoided. For example, when an aqueous solution containing methylene blue is processed using an integrated membrane, a large flux of 200 L m-2 h-1 and a stable permeating selectivity of 85% were achieved. The combined photocatalysis and filtration function leads to superior performance of the integrated membranes, which have a potential to be used for the removal of organic pollutants in drinking water.

Synthesis, characterization and activity of an immobilized photocatalyst : natural porous diatomite supported titania nanoparticles

Diatomite, a porous non-metal mineral, was used as support to prepare TiO2/diatomite composites by a modified sol–gel method. The as-prepared composites were calcined at temperatures ranging from 450 to 950 _C. The characterization tests included X-ray powder diffraction (XRD), scanning electron microscopy (SEM) with an energy-dispersive X-ray spectrometer (EDS), high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), and nitrogen adsorption/desorption measurements. The XRD analysis indicated that the binary mixtures of anatase and rutile exist in the composites. The morphology analysis confirmed the TiO2 particles were uniformly immobilized on the surface of diatom with a strong interfacial anchoring strength, which leads to few drain of photocatalytic components during practical applications. In further XPS studies of hybrid catalyst, we found the evidence of the presence of Ti–O–Si bond and increased percentage of surface hydroxyl. In addition, the adsorption capacity and photocatalytic activity of synthesized TiO2/diatomite composites were evaluated by studying the degradation kinetics of aqueous Rhodamine B under UV-light irradiation. The photocatalytic degradation was found to follow pseudo-first order kinetics according to the Langmuir–Hinshelwood model. The preferable removal efficiency was observed in composites by 750 _C calcination, which is attributed to a relatively appropriate anatase/rutile mixing ratio of 90/10.

Fabrication of macro–mesoporous titania/alumina core–shell materials in oil/water interface

A series of macro–mesoporous TiO2/Al2O3 nanocomposites with different morphologies were synthesized. The materials were calcined at 723 K and were characterized by X-ray diffraction (XRD), Scanning electron microscopy (SEM), Transmission electron microscope (TEM), N2 adsorption/desorption, Infrared Emission Spectroscopy (IES), X-ray photoelectron spectroscopy (XPS) and UV–visible spectroscopy (UV–visible). A modified approach was proposed for the synthesis of 1D (fibrous) nanocomposite with higher Ti/Al molar ratio (2:1) at lower temperature (<100 °C), which makes it possible to synthesize such materials on industrial scale. The performance–morphology relationship of as-synthesized TiO2/Al2O3 nanocomposites was investigated by the photocatalytic degradation of a model organic pollutant under UV irradiation. The samples with 1D (fibrous) morphology exhibited superior catalytic performance than the samples without, such as titania microspheres.

Use of Polyazaheterocycles in the Assembly of New Cadmium Sulfate Frameworks: Synthesis, Structure, and Properties

The reaction of cadmium sulfate in the presence of polyazaheterocyclic organic molecules gave rise to a variety of new cadmium sulfate phases in water containing solvothermal reaction. The compounds have two- (I) and three-dimensionally (II-VI) extended structures. All the compounds have structures built up by the connectivity involving the cadmium octahedra and the sulfate tetrahedra in which the heterocyclic organic molecules act as the ligand. The linkages between the Cd2+ and (SO4)2- ions form one- (II), two- (I, III, and IV), and three- (V and VI) dimensionally extended cadmium sulfate phases. The connectivity between Cd2+ ion and the heterocyclic ligand also gives rise to one- and two-dimensional structures. The inter-connectivity between the two units gives rise to the observed structures. The presence of Cd-O-Cd chains and Cd-O-Cd layers in some of the structures is noteworthy. The adsorption/desorption studies suggest that the cadmium sulfate phases adsorb/desorb anionic dyes selectively in the presence of water/ethanol, respectively. The photocatalytic degradation studies on cationic dyes under UV-irradiation indicate modest activity. The cyanosilylation of imines using the present compounds as heterogeneous catalyst indicate good catalytic behavior. The various properties exhibited by the cadmium sulfate phases suggest that these compounds are versatile. All the compounds were characterized by powder X-ray diffraction, thermogravimetric analysis, infrared (IR) and UV-visible studies.

Combustion Synthesized Vanadia Rods for Environmental Applications

Rod-shaped V(2)O(5) was synthesized using the solution combustion technique, and the morphology of the compound was confirmed by TEM. Rods of an average diameter of 500 nm and length 3-6 times the diameter were obtained after the calcination of freshly prepared V(2)O(5) at 550 degrees C for 24 h. Pd metal nanoparticles of 20 nm size were deposited onto the rods using the wet impregnation technique. The as-synthesized, calcined and Pd impregnated V(2)O(5) were characterized by a wide variety of techniques including energy dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy. These compounds were tested for CO oxidation, adsorption, and photocatalytic degradation of dyes. The 1% Pd/V(2)O(5) showed a high activity for CO oxidation, the as-synthesized compound showed activity for the adsorption of cationic dyes, whereas the calcined V(2)O(5) sample showed high rates of photocatalytic degradation of dyes. (C) 2010 American Institute of Chemical Engineers AIChE J, 57: 2215-2228, 2011

Electrochemical sensing and photocatalysis using Ag-TiO2 microwires

Anatase Ag-TiO2 microwires with high sensitivity and photocatalytic activity were synthesized via polyol synthesis route followed by a simple surface modification and chemical reduction approach for attachment of silver. The superior performance of the Ag-TiO2 composite microwires is attributed to improved surface reactivity, mass transport and catalytic property as a result of wiring the TiO2 surface with Ag nanoparticles. Compared to the TiO2 microwires, Ag-TiO2 microwires exhibited three times higher sensitivity in the detection of cationic dye such as methylene blue. Photocatalytic degradation efficiency was also found to be significantly enhanced at constant illumination protocols and observation times. The improved performance is attributed to the formation of a Schottky barrier between TiO2 and Ag nanoparticles leading to a fast transport of photogenerated electrons to the Ag nanoparticles.

Morphology control synthesis of Au-Cu2S metal-semiconductor hybrid nanostructures by modulating reaction constituents

A facile methodology for synthesizing Au-Cu2S hybrid nanoparticles is presented. Au-Cu2S nanoparticles have application in visible light driven photocatalytic degradation of dyes. Detailed microstructural and compositional characterization illustrated that the hybrid nanoparticles are composed of cube shaped Au-Cu solid solution and hemispherical shaped Cu2S phases. Investigation of nanoparticles extracted at different stages of the synthesis process revealed that the mechanism of formation of hybrid nanoparticles involved initial formation of isolated cube shaped pure Au nanoparticles and Cu-thiolate complex. In the subsequent stages, the Au nanoparticles get adsorbed onto the Cu-thiolate complex which is followed by the decomposition of the Cu-thiolate complex to form Au-Cu2S hybrid nanoparticles. This study also illustrates that an optimum concentration of dodecanethiol is required both for achieving size and morphological uniformity of the participating phases and for their attachment to form a hybrid nanoparticle.

Descoloração e Mineralização de Corantes Reativos por Processo Fotocatalítico Utilizando ZnO e Radiação UV

As indústrias consomem volumes elevados de água e outras substâncias químicas na síntese dos seus produtos e geram grande quantidade de rejeitos. Entre os mais importantes poluentes encontrados nos efluentes dessas indústrias estão os corantes sintéticos que representam um problema, pois não são facilmente destruídos por tratamentos convencionais. A fotocatálise heterogênea tem sido considerada como uma alternativa efetiva no tratamento de efluentes contendo esses corantes. Neste trabalho, estudou-se a cinética de descoloração e o grau de mineralização dos corantes sintéticos reativos Yellow 145, Black 5, Red 4 e Blue 21 através da fotocatálise utilizando ZnO puro e impregnado com íons Fe2+ e Co2+. Testes preliminares foram realizados para otimizar a concentração dos corantes e a massa mínima de catalisador a ser utilizado nos experimentos fotocatalíticos. Além da fotocatálise, experimentos individuais de fotólise e adsorção também foram realizados, porém se mostraram poucos eficientes. Através da espectrofotometria UV-Vis, verificou-se o total descoramento individual dos corantes em aproximadamente 30 minutos de irradiação com ZnO. O grau de mineralização de cada corante foi determinado através de análise de carbono orgânico total (COT), atingindo-se cerca de 70 a 80% de mineralização após 240 minutos de tratamento fotocatalítico. Foram comparadas, ainda, as eficiências de cada fotocatalisador ZnO, Fe/ZnO e Co/ZnO na mineralização de uma solução contendo a mistura dos quatro corantes já mencionados após 240 minutos de reação. A eficiência na mineralização da mistura dos corantes seguiu a seguinte ordem: Co/ZnO (32%), ZnO (78%) e Fe/ZnO (87%). A reação de degradação fotocatalítica do corante Black 5 seguiu uma cinética de primeira ordem, enquanto que os corantes Yellow 145, Red 4 e Blue 21 seguiram uma cinética de ordem zero.

Degradação de corantes têxteis ácidos e reativos por fotocatálise heterogênea, usando TiO2 como fotocatalisador

A indústria têxtil tem como característica a geração de grandes volumes de resíduos, principalmente corantes oriundos do tingimento de fios e tecidos. Os tratamentos convencionais de efluentes têxteis são ineficazes na degradação da maioria dos corantes. A fotocatálise heterogênea vem surgindo como alternativa promissora no tratamento desses poluentes. Neste trabalho, estudou-se a degradação fotocatalítica de duas soluções, simuladas em laboratório, compostas pelos corantes ácidos Blue 74, Red 51 e Yellow 3 (efluente I) e pelos reativos Black 5, Red 239 e Yellow 17 (efluente II), além de outros produtos químicos. Testes preliminares foram realizados para otimizar o pH e a massa de catalisador (TiO2) utilizados. Além da fotocatálise, experimentos de fotólise e adsorção também foram realizados. Através de espectrofotometria UV-VIS, verificou-se um descoramento por fotocatálise de 96% em 240 min e 97% em 30 min dos efluentes I e II, respectivamente. A mineralização do efluente I foi baixa (37%) e a do efluente II desprezível, nos tempos utilizados. No banho com corantes ácidos, foram realizadas ainda análises de toxicidade com sementes de alface (Lactuca sativa). A CE50 inicial estimada foi igual a 19,28 %, sendo a toxicidade totalmente removida após 63 min de processo fotocatalítico. A fotólise não obteve a mesma eficiência da fotocatálise, mostrando a importância do catalisador na degradação. A adsorção não foi significativa para os efluentes estudados. As cinéticas de degradação fotocatalítica de todos os corantes seguiram um modelo de pseudo-primeira ordem