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The electrochemical oxidation of organics in water performed in micro reactors on boron doped diamond (BDD) anode was investigated both theoretically and experimentally in order to find the influence of various operative parameters on the conversion and the current efficiency CE of the process. The electrochemical oxidation of formic acid (FA) was selected as a model case. High conversions for a single passage of the electrolytic solution inside the cell were obtained by operating with proper residence times and low distances between cathode and anode. The effect of initial concentration, flow rate and current density was investigated in detail. Theoretical predictions were in very good agreement with experimental results for both mass transfer control, oxidation reaction control and mixed kinetic regimes in spite of the fact that no adjustable parameters was used. Mass transfer process was successfully modelled by considering for simplicity a constant Sh number (e.g., a constant mass transfer coefficient k m) for a process performed with no high values of the current intensity to minimize the effect of the gas bubbling on the flowdynamic pattern. For mixed kinetic regimes, two different modelling approaches were used. In the first one, the oxidation of organics at BDD was assumed to be mass transfer controlled and to occur with an intrinsic 100% CE when applied current density is higher than the limiting current density. In the second case, the CE of the process was modelled assuming that the competition between organic and water oxidation depends only on the electrodic material and on the nature and the concentration of the organic. In the latter case a better agreement between experimental data and theoretical predictions was observed. © 2011 Elsevier Ltd. All rights reserved

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The performances of reverse electrodialysis depend on several factors, including the nature of the electrode material and of the redox processes adopted to make possible the conversion between chemical potential and electric power. In this paper the possible utilization of various redox processes (reduction/oxidation of iron species, oxidation and reduction of water, oxidation of chlorine and reduction of water) was studied in a stack equipped with 10-50 cell pairs and by focused electrolyses in a three compartment cell. The effect of selected redox processes on power density output and eventual contamination of saline solutions flowing in the stack was evaluated in detail. The effect of the number of cell pairs and of the concentration of saline solutions was also investigated.

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Sensitized P25 TiO2 was prepared by wet impregnation with a home-prepared perylene dye, i.e., N,N'-bis(2-(1-piperazino)ethyl)-3,4,9,10-perylene-tetracarboxylic acid diimide dichloride (PZPER). Energy levels of PZPER were found to be compatible with those of TiO2 allowing fast electron transfer. The obtained catalyst has been characterized and used in the gas-phase partial oxidation of aliphatic primary and secondary alcohols, i.e., methanol, ethanol, and 2-propanol. The reaction was carried out under cut-off (λ > 400 nm) simulated solar radiation in O2 atmosphere. The perylene derivative allowed a good absorbance of visible radiation thanks to its low optical energy gap (2.6 eV) which was evaluated by cyclic voltammetry. The optimal organic sensitizing amount was found to be 5.6 % w/w in terms of yield in carbonyl derivatives. Moreover, no change in reactivity/selectivity was observed after 10-h irradiation thus confirming the catalyst stability. Yields into formaldehyde, acetaldehyde, and acetone were 67, 70, and 96 %, respectively. No significant amounts of organic byproducts were detected but for methanol oxidation, whereas a minor amount of the substrate degraded to CO2.