Photoelectrocatalysis: Principles, nanoemitter applications and routes to bio-inspired systems

An overview on processes that are relevant in light-induced fuel generation, such as water photoelectrolysis or carbon dioxide reduction, is given. Considered processes encompass the photophysics of light absorption, excitation energy transfer to catalytically active sites and interfacial reactions at the catalyst/solution phase boundary. The two major routes envisaged for realization of photoelectrocatalytic systems, e.g. bio-inspired single photon catalysis and multiple photon inorganic or hybrid tandem cells, are outlined. For development of efficient tandem cell structures that are based on non-oxidic semiconductors, stabilization strategies are presented. Physical surface passivation is described using the recently introduced nanoemitter concept which is also applicable in photovoltaic (solid state or electrochemical) solar cells and first results with p-Si and p-InP thin films are presented. Solar-to-hydrogen efficiencies reach 12.1% for homoepitaxial InP thin films covered with Rh nanoislands. In the pursuit to develop biologically inspired systems, enzyme adsorption onto electrochemically nanostructured silicon surfaces is presented and tapping mode atomic force microscopy images of heterodimeric enzymes are shown. An outlook towards future envisaged systems is given. © 2010 The Royal Society of Chemistry.

Synthesis and characterization of Fe(III)-doped ceramic membranes of titanium dioxide and its application in photoelectrocatalysis of a textile dye

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

Photoelectrocatalysis based on Ti/TiO2 nanotubes removes toxic properties of the azo dyes Disperse Red 1, Disperse Red 13 and Disperse Orange 1 from aqueous chloride samples

This work describes the efficiency of photoelectrocatalysis based on Ti/TiO2 nanotubes in the degradation of the azo dyes Disperse Red 1, Disperse Red 13 and Disperse Orange 1 and to remove their toxic properties, as an alternative method for the treatment of effluents and water. For this purpose, the discoloration rate, total organic carbon (TOC) removal, and genotoxic, cytotoxic and mutagenic responses were determined, using the comet, micronucleus and cytotoxicity assays in HepG2 cells and the Salmonella mutagenicity assay. In a previous study it was found that the surfactant Emulsogen could contribute to the low mineralization of the dyes (60% after 4h of treatment), which, in turn, seems to account for the mutagenicity of the products generated. Thus this surfactant was not added to the chloride medium in order to avoid this interference. The photoelectrocatalytic method presented rapid discoloration and the TOC reduction was ≥87% after 240min of treatment, showing that photoelectrocatalysis is able to mineralize the dyes tested. The method was also efficient in removing the mutagenic activity and cytotoxic effects of these three dyes. Thus it was concluded that photoelectrocatalysis was a promising method for the treatment of aqueous samples. © 2013 Elsevier Ltd.

Photoelectrocatalytic treatment of p-nitrophenol using Ti/TiO2 thin-film electrode

The photoelectrochemical degradation of p-nitrophenol (PNP) was investigated using titanium dioxide thin-film photoelectrode. The effects of different supporting electrolytes, pH, applied potential and PNP concentration were examined and discussed. Complete photodegradation was obtained in perchlorate medium at pH 2 when the photoanode was biased at +1.0 V (versus SCE) during a 3-h experiment. Under these conditions, carbon removal of approximately 60% was achieved. (C) 2005 Elsevier B.V. All rights reserved.

Toxicity assessment and degradation of disperse azo dyes by photoelectrocatalytic oxidation on Ti/TiO2 nanotubular array electrodes

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Photoelectrocatalytic Removal of Bromate Using Ti/TiO2 Coated as a Photocathode

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

Mutagenic activity removal of selected disperse dye by photoeletrocatalytic treatment

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

Inactivation and disposal of by-products from Mycobacterium smegmatis by photoelectrocatalytic oxidation using Ti/TiO2-Ag nanotube electrodes

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

Evaluation of the photoelectrocatalytic method for oxidizing chloride and simultaneous removal of microcystin toxins in surface waters

The production of chlorine was investigated in the photoelectrocatalytic oxidation of a chloride-containing solution using a TiO(2) thin-film electrode biased at current density from 5 to 50 mA cm(-2) and illuminated by UV light. Such parameters as chloride concentrations from 0.001 to 0.10 mol L(-1), pH 2-12, and interfering salts were varied in this study in order to determine their effect on this oxidation process. At an optimum condition this photoelectrocatalytic method can produce active chlorine at levels compatible to water disinfections processes using a chloride concentration higher than 0.010 mol L(-1) at a pH of 4 and a current density of 30 mA cm(-2). The method was successfully applied to treat surface water collected from a Brazilian river. After 150 min of photoelectrocatalytic oxidation, we obtained a 90% reduction in total organic carbon removal, a 100% removal of turbidity, a 93% decrease in colour and a chemical oxygen demand (COD) removal of around 96% (N=3). The proposed technology based on photoelectrocatalytic oxidation was also tested in treating 250 mL of a solution containing 0.05 mol L(-1) NaCl and 50 mu g L(-1) of Microcystin aeruginosa. The bacteria is completely removed after 5 min of photoelectrocatalysis following an initial rate constant removal of -0.260 min(-1), suggesting that the present method could be considered as a promising alternative to chlorine-based disinfections. (C) 2008 Elsevier Ltd. All rights reserved.

Photoeletrocatalytic oxidation of anionic surfactant used in leather industry on nanoporous Ti/TiO2 eletrodes

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

Simultaneous removal of chromium and leather dye from simulated tannery effluent by photoelectrochemistry

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

Nanoporous of W/WO3 Thin Film Electrode Grown by Electrochemical Anodization Applied in the Photoelectrocatalytic Oxidation of the Basic Red 51 used in Hair Dye

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

Assessment of by-products of chlorination and photoelectrocatalytic chlorination of an azo dye

The present work describes a more efficient methodology for the chlorination of water containing disperse dyes, where the chlorinated byproducts identified by mass spectra are compared. this investigation, we tested the degradation of Cl Disperse Blue 291 dye, 2-[(2-Bromo-4,6-dinitrophenyl)azo]-5-(diethylamino)-4-methoxyacetanilide) a commercial azo dye with mutagenic properties. The present work evaluates the photoelectrocatalytic efficiency of removing the Cl Disperse Blue 291 dye from a wastewater of the textile industry. We employed NaCl as a supporting electrolyte. It should be noted that photoelectrocatalytic techniques are non-conventional method of generating chlorine radicals. The by-products formed in this process were analyzed using spectrophotometry, liquid chromatography, dissolved organic carbon, mass spectral analysis and mutagenicity assays. The process efficiency was compared with the conventional chlorination process adopted during sewage and effluents treatment processes. This conventional chlorination process is less efficient in removing color, total organic carbon than the photoelectrochemistry technique. Furthermore, we shall demonstrate that the mutagenicity of the generated by-products obtained using photoelectrocatalysis is completely different from that obtained by the conventional oxidation of chloride ions in the drinking wafer treatment process. (C) 2012 Published by Elsevier B.V.

Highly ordered TiO2 nanotube arrays and photoelectrocatalytic oxidation of aromatic amine

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

Evaluation of different electrochemical methods on the oxidation and degradation of Reactive Blue 4 in aqueous solution

The oxidation of a reactive dye, Reactive Blue 4, RB4, (C.I. 61205), widely used in the textile industries to color natural fibers, was studied by electrochemical techniques. The oxidation on glassy carbon electrode and reticulated vitreous carbon electrode occurs in only one step at 2.0 < PH < 12 involving a two-electron transfer to the amine group leading to the imide derivative. Dye solution was not decolorized effectively in this electrolysis process. Nevertheless, the oxidation of this dye on Ti/SnO2/SbOx (3% mol)/RuO2 (1% mol) electrode showed 100% of decolorization and 60% of total organic carbon removal in Na2SO4 0.2 M at PH 2.2 and potential of +2.4 V. Experiments on degradation photoelectrocatalytic were also carried out for RB4 degradation in Na2SO4 0.1 K PH 12, using a Ti/TiO2 photoanode biased at +1.0 V and UV light. After 1 h of electrolysis the results indicated total color removal and 37% of mineralization. (c) 2004 Elsevier Ltd. All rights reserved.