Sulphur vs NH Group: Effects on the CO2 Electroreduction Capability of Phenylenediamine-Cp Cobalt Complexes.

The cobalt complex (I) with cyclopentadienyl and 2-aminothiophenolate ligands was investigated as a homogeneous catalyst for electrochemical CO2 reduction. By comparing its behavior with an analogous complex with the phenylenediamine (II), the effect of sulfur atom as a substituent has been evaluated. As a result, a positive shift of the reduction potential and the reversibility of the corresponding redox process have been observed, also suggesting a higher stability of the compound with sulfur. Under anhydrous conditions, complex I showed a higher current enhancement in the presence of CO2 (9.41) in comparison with II (4.12). Moreover, the presence of only one -NH group in I explained the difference in the observed increases on the catalytic activity toward CO2 due to the presence of water, with current enhancements of 22.73 and 24.40 for I and II, respectively. DFT calculations confirmed the effect of sulfur on the lowering of the energy of the frontier orbitals of I, highlighted by electrochemical measurements. Furthermore, the condensed Fukui function f - values agreed very well with the current enhancement observed in the absence of water.

Mechanistic insights into 2,4-D photoelectrocatalytic removal from water with TiO2 nanotubes under dark and solar light irradiation.

Removal of recalcitrant pollutants from water is a major challenge, to which the photoelectrocatalytic processes may be a solution. Applied potential plays a key role in the photocatalytic activity of the semiconductor. This paper investigated the effect of applied potential on the photoelectrocatalytic oxidation of 2,4-Dichlorophenoxyacetic acid (2,4-D) with TiO2 nanotubular anodes under solar light irradiation. The process was investigated at constant potentials in different regions of the polarization curve: the ohmic region, the saturation region and in the region of the Schottky barrier breakdown. PEC tests were performed in aqueous solutions of 2,4-D, and in the presence of methanol or formic acid, as scavengers of OH• radicals and holes. Results showed the main mechanism is oxidation by OH• radicals from water oxidation, while runs with hole scavenger revealed a second mechanism of direct oxidation by holes photogenerated at the electrode surface, with high removal rates due to current doubling effect.

Experimental study on the optimisation of azo-dyes removal by photo-electrochemical oxidation with TiO2 nanotubes.

An experimental investigation is here presented on the photo-electrochemical removal of Methyl Orange (MO), selected as a model of the organic dyes, contained in wastewaters. The process is carried out in an electrochemical flow reactor, in which titania nanotubular electrode is irradiated with a simulated solar light. Design of Experiments (DOE) technique is used to plan the experimental campaign and investigate on the single and combined effects of applied current, electrolyte flow rate, and initial MO concentration, on the specific reaction rate. The results of the DOE analysis, also combined with the study of the distribution of the intermediate products, confirm a reaction mechanism mediated by OH radicals; high applied current and low reactant concentration resulted as favourable conditions to achieve high specific reaction rate of color removal.

Toward an accurate quantification in atom probe tomography reconstruction by correlative electron tomography approach on nanoporous materials.

In this contribution, we propose a protocol for analysis and accurate reconstruction of nanoporous materials by atom probe tomography (APT). The existence of several holes in porous materials makes both the direct APT analysis and reconstruction almost inaccessible. In the past, a solution has been proposed by filling pores with electron beam-induced deposition. Here, we present an alternative solution using an electro-chemical method allowing to fill even small and dense pores, making APT analysis possible. Concerning the 3D reconstruction, the microstructural features observed by electron tomography are used to finely calibrate the APT reconstruction parameters.

4-Nitrobenzene Grafted in Porous Silicon: Application to Optical Lithography.

In this work, we report a method to process porous silicon to improve its chemical resistance to alkaline solution attacks based on the functionalization of the pore surface by the electrochemical reduction of 4-nitrobenzendiazonium salt. This method provides porous silicon with strong resistance to the etching solutions used in optical lithography and allows the fabrication of tailored metallic contacts on its surface. The samples were studied by chemical, electrochemical, and morphological methods. We demonstrate that the grafted samples show a resistance to harsh alkaline solution more than three orders of magnitude larger than that of pristine porous silicon, being mostly unmodified after about 40 min. The samples maintained open pores after the grafting, making them suitable for further treatments like filling by polymers. Optical lithography was performed on the functionalized samples, and electrochemical characterization results are shown.

Electrochemical treatment of water containing Microcystis aeruginosa in a fixed bed reactor with three-dimensional conductive diamond anodes.

An electrochemical treatment was investigated to remove Microcystis aeruginosa from water. A fixed bed reactor in flow was tested, which was equipped with electrodes constituted by stacks of grids electrically connected in parallel, with the electric field parallel to the fluid flow. Conductive diamond were used as anodes, platinised Ti as cathode. Electrolyses were performed in continuous and in batch recirculated mode with flow rates corresponding to Re from 10 to 160, current densities in the range 10-60Am(-2) and Cl(-) concentrations up to 600gm(-3). The absorbance of chlorophyll-a pigment and the concentration of products and by-products of electrolysis were measured. In continuous experiments without algae in the inlet stream, total oxidants concentrations as equivalent Cl2, of about 0.7gCl2m(-3) were measured; the maximum values were obtained at Re=10 and i=25Am(-2), with values strongly dependent on the concentration of Cl(-). The highest algae inactivation was obtained under the operative conditions of maximum generation of oxidants; in the presence of microalgae the oxidants concentrations were generally below the detection limit. Results indicated that most of the bulk oxidants electrogenerated is constituted by active chlorine. The prevailing mechanism of M. aeruginosa inactivation is the disinfection by bulk oxidants. The experimental data were quantitatively interpreted through a simple plug flow model, in which the axial dispersion accounts for the non-ideal flow behaviour of the system; the model was successfully used to simulate the performances of the reactor in the single-stack configuration used for the experiments and in multi-stack configurations.

Electrochemical treatment of phenolic waters in presence of chloride with boron-doped diamond (BDD) anodes: experimental study and mathematical model.

This work deals with an experimental and numerical study on the electrochemical treatment of waters containing phenolic compounds with boron-doped diamond (BDD) anodes. Anodic oxidation of m-cresol, as a model of phenolic compound, was investigated by galvanostatic electrolyses. The electrolyses were carried out under different experimental conditions by using an impinging-jet flow cell inserted in a hydraulic circuit in a closed loop. On the basis of the experimental results a mathematical model was implemented to simulate the effect of the chemistry of organic compounds and solution on the process, in particular the effect of chlorides on the kinetics of m-cresol oxidation. The effect of hydrodynamics of the cell on the mass transfer towards the electrode surface was also considered. The model was validated through comparison with experimental data: the results showed that the proposed model well interpreted the complex effect on removal efficiency of such operative parameters as current density, hydrodynamic of the reactor and chemistry of the solution. The model predictions were utilised to obtain quantitative information on the reaction mechanism, as well as to predict the performance of the process under different operative conditions, by calculating some relevant figures of merit.

Electrokinetic removal of 2,6-dichlorophenol and diuron from kaolinite and humic acid-clay system.

This paper presents the results of a study on the electrokinetic treatment of kaolinite and humic acid kaolinite complexes spiked with 2,6-dichlorophenol or 3-(3,4-dichlorophenyl)-1,1-dimethylurea (diuron). In particular, the attention was paid to the interaction between solid surface and dissolved organics: the effects of contaminant sorption as well as the physicochemical reactions on the efficiency of electrokinetic remediation were investigated. Using a 3V/cm voltage gradient, approximately 90% of diuron was removed from kaolinite after one water pore volume was collected in the cathode reservoir, but much lower efficiency was obtained in the electrokinetic removal of this compound from humic acid-coated kaolinite. The results also showed that partial degradation of the contaminant occurred during electrokinetic treatment of kaolinite clay spiked with 2,6-dichlorophenol: the contamination in the clay could be remediated by the combination of electrokinetic extraction and electrochemical reactions.

Application of electrochemical reactors for industrial waste-water treatment.

The effectiveness of electrochemical reactors for industrial wastewater treatment has been improved since three-dimensional electrodes have been introduced; in fact, limitations of mass transfer can arise, due to the low concentrations of pollutants which may be involved in the process. Three-dimensional electrodes offer a very high electrode area per unit electrode volume and they can act as turbulence promoters or give rise to high linear electrolyte velocity, resulting in high values of mass transport coefficient. However, careful selection of operative parameters is needed in order to obtain high performance. This paper examines the results obtained in our laboratory on the cathodic reduction of copper at RVC electrodes; in particular the interference of dissolved oxygen is studied during the removal of copper from extremely diluted solutions (C < 10 ppm). Some results are also discussed on the removal of organic pollutants by electrochemical oxidation at three-dimensional anode consisting of a fixed bed of carbon pellets.

Electrochemical oxidation of phenolic and other organic compounds at boron doped diamond electrodes for wastewater treatment: effect of mass transfer.

The paper presents the results of an experimental study on oxidation at boron doped diamond electrodes (BDD) of some phenolic compounds: phenol (PH), para-hydroxibenzoic acid (PHB), cathecole (CT), hydroquinone (HQ) are considered, singularly contained in aqueous solutions or in the presence of glucose (G), which was selected to represent the class of biodegradable compounds. Oxidation of benzoquinone (BQ) and maleic acid (MA), generally detected as intermediates products from phenol degradation, is also investigated. Great attention is paid to verify the feasibility of a selective process in which the oxidation is specifically addressed to the phenolic fraction up to non toxic intermediate products which are more biodegradable than the original phenols.

Electrochemical oxidation of p-hydroxybenzoic and protocathecuic acids at a dimensional stable anode (DSA) in the presence of NaCl.

This work is part of a wider research programme on innovative technologies for industrial wastewater treatment. Results from electrolyses at DSA commercial anodes of synthetic solutions with composition analogous to that of agro-industrial wastes are presented. The results obtained indicate that the rate of degradation of phenolic compounds is high, provided that chloride ions are present in solution. Oxidation of phenolic compounds is faster than that of biodegradable substances, such as sugars or amminoacids. Moreover, investigation on the trend of toxicity during the treatment, seems to exclude that toxic intermediates persist in solution when phenolic compounds are removed. Experiments on olive oil mill wastewater (OMW) samples show that the results obtained from synthetic solutions are extensible to real wastewater. When phenolic compounds are completely removed, the toxicity of the solution is very low; the initial dark colour of the solution, due to the brown pigment which characterises OMW, is nearly completely disappeared.