Arc Synthesis, Crystal Structure, and Photoelectrochemistry of Copper(I) Tungstate.

A little-studied p-type ternary oxide semiconductor, copper(I) tungstate (Cu2WO4), was assessed by a combined theoretical/experimental approach. A detailed computational study was performed to solve the long-standing debate on the space group of Cu2WO4, which was determined to be triclinic P1. Cu2WO4 was synthesized by a time-efficient, arc-melting method, and the crystalline reddish particulate product showed broad-band absorption in the UV-visible spectral region, thermal stability up to ∼260 °C, and cathodic photoelectrochemical activity. Controlled thermal oxidation of copper from the Cu(I) to Cu(II) oxidation state showed that the crystal lattice could accommodate Cu2+ cations up to ∼260 °C, beyond which the compound was converted to CuO and CuWO4. This process was monitored by powder X-ray diffraction and X-ray photoelectron spectroscopy. The electronic band structure of Cu2WO4 was contrasted with that of the Cu(II) counterpart, CuWO4 using spin-polarized density functional theory (DFT). Finally, the compound Cu2WO4 was determined to have a high-lying (negative potential) conduction band edge underlining its promise for driving energetic photoredox reactions.

Remediation of 17-α-ethinylestradiol aqueous solution by photocatalysis and electrochemically-assisted photocatalysis using TiO2 and TiO2/WO3 electrodes irradiated by a solar simulator.

TiO2 and TiO2/WO3 electrodes, irradiated by a solar simulator in configurations for heterogeneous photocatalysis (HP) and electrochemically-assisted HP (EHP), were used to remediate aqueous solutions containing 10 mg L(-1) (34 µmol L(-1)) of 17-α-ethinylestradiol (EE2), active component of most oral contraceptives. The photocatalysts consisted of 4.5 µm thick porous films of TiO2 and TiO2/WO3 (molar ratio W/Ti of 12%) deposited on transparent electrodes from aqueous suspensions of TiO2 particles and WO3 precursors, followed by thermal treatment at 450 (°)C. First, an energy diagram was organized with photoelectrochemical and UV-Vis absorption spectroscopy data and revealed that EE2 could be directly oxidized by the photogenerated holes at the semiconductor surfaces, considering the relative HOMO level for EE2 and the semiconductor valence band edges. Also, for the irradiated hybrid photocatalyst, electrons in TiO2 should be transferred to WO3 conduction band, while holes move toward TiO2 valence band, improving charge separation. The remediated EE2 solutions were analyzed by fluorescence, HPLC and total organic carbon measurements. As expected from the energy diagram, both photocatalysts promoted the EE2 oxidation in HP configuration; after 4 h, the EE2 concentration decayed to 6.2 mg L(-1) (35% of EE2 removal) with irradiated TiO2 while TiO2/WO3 electrode resulted in 45% EE2 removal. A higher performance was achieved in EHP systems, when a Pt wire was introduced as a counter-electrode and the photoelectrodes were biased at +0.7 V; then, the EE2 removal corresponded to 48 and 54% for the TiO2 and TiO2/WO3, respectively. The hybrid TiO2/WO3, when compared to TiO2 electrode, exhibited enhanced sunlight harvesting and improved separation of photogenerated charge carriers, resulting in higher performance for removing this contaminant of emerging concern from aqueous solution.

Degradation of acid blue 40 dye solution and dye house wastewater from textile industry by photo-assisted electrochemical process.

In this paper, electrochemical and photo-assisted electrochemical processes are used for color, total organic carbon (TOC) and chemical oxygen demand (COD) degradation of one of the most abundant and strongly colored industrial wastewaters, which results from the dyeing of fibers and fabrics in the textile industry. The experiments were carried out in an 18 L pilot-scale tubular flow reactor with 70%TiO(2)/30%RuO(2) DSA. A synthetic acid blue 40 solution and real dye house wastewater, containing the same dye, were used for the experiments. By using current density of 80 mA cm(-2) electrochemical process has the capability to remove 80% of color, 46% of TOC and 69% of COD. When used the photochemical process with 4.6 mW cm(-2) of 254 nm UV-C radiation to assist the electrolysis, has been obtained 90% of color, 64% of TOC and 60% of COD removal in 90 minutes of processing; furthermore, 70% of initial color was degraded within the first 15 minutes. Experimental runs using dye house wastewater resulted in 78% of color, 26% of TOC and 49% of COD in electrolysis at 80 mA cm(-2) and 90 min; additionally, when photo-assisted, electrolysis resulted in removals of 85% of color, 42% of TOC and 58% of COD. For the operational conditions used in this study, color, TOC and COD showed pseudo-first-order decaying profiles. Apparent rate constants for degradation of TOC and COD were improved by one order of magnitude when the photo-electrochemical process was used.

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide: study for the degradation of 2,4-dichlorophenoxyacetic acid.

This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode, and the optimization of the O2 reduction rate relative to cell potential. A study for the simultaneous oxidation of the herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) by the in situ electrogenerated H2O2 is also reported. Experiments were performed in 0.3 M of K2SO4, pH of 10 and 3.5. Oxygen concentration in solution was kept in 25 mg L(-1). Maximum hydrogen peroxide generation rate was reached at -1.6 V versus SCE for both, acidic and alkaline solutions. Then, 100 mg L(-1) of 2,4-D was added to the solution. First order apparent rate constants for 2,4-D degradation ranged from 0.9 to 6.3x10(-5) m s(-1), depending on the catalyst used (UV or UV+Fe(II)). TOC reduction was favored in acidic medium where a decreasing of 69% of the initial concentration was observed in the process catalyzed by UV+Fe(II). This figure was an indication that some of the intermediates derived from 2,4-D decomposition remained in solution, mainly as lighter aliphatic compounds.

Electrodegradation of landfill leachate in a flow electrochemical reactor.

Sanitary landfills are the major method used today for the disposal and management of municipal solid waste. Decomposition of waste and rainfall generate leachate at the bottom of landfills, causing groundwater contamination. In this study, leachate from a municipal landfill site was treated by electrochemical oxidation in a pilot scale flow reactor, using oxide-coated titanium anode. The experiments were conducted under a constant flow rate of 2000 lh(-1) and the effect of current density on chemical oxygen demand, total organic carbon, color and ammonium removal was investigated. At a current density of 116.0 mA cm(-2) and 180 min of processing, the removal rates achieved were 73% for COD, 57% for TOC, 86% for color and 49% for ammonium. The process proved effective in degrading leachate, despite this effluent's usual refractoriness to treatment.