Routes for the electrochemical degradation of the artificial food azo-colour Ponceau 4R by advanced oxidation processes

The performance of three electrochemical advanced oxidation processes, namely electro-oxidation with electrogenerated H2O2 (EO-H2O2), electro-Fenton (EF) and photoelectro-Fenton (PEF) for the treatment of aqueous solutions of the food azo dye Ponceau 4R in an undivided cell with a BDD anode and an air-diffusion cathode was compared in terms of colour, dye concentration and total organic carbon (TOC) removals. PEF treatments in ultrapure water with Na2SO4 were performed to assess the effect of current density, as well as supporting electrolyte and dye concentrations. At 100 mA cm-2, solutions of 130 mL of 254 mg L-1 of the dye in 0.05 M Na2SO4 became colourless and totally mineralized after 50 and 240 min, respectively, which can be explained by the synergistic action of BDD(¿OH) at the anode surface and homogeneous ¿OH formed in the bulk from Fenton's reaction promoted in the presence of Fe2+ catalyst. Furthermore, UVA photons induced the continuous Fe2+ regeneration and photolytic decomposition of refractory intermediate complexes. In that aqueous matrix, the cleavage of the dye molecules proceeded through several reaction routes to yield N-containing and non-N-containing derivatives with one or two aromatic rings, short-chain aliphatic carboxylic acids and inorganic ions. Oxalic and oxamic acids and sulfate ions were accumulated at different rates in EO-H2O2, EF and PEF. The three methods allowed the progressive decontamination of Ponceau 4R solutions in a real water matrix even without the addition of electrolyte, although complete TOC abatement after 360 min at 33.3 mA cm-2 was only ensured by the iron-catalyzed PEF process

Effects of the electrodeposition time in the synthesis of carbon-supported Pt(Cu) and Pt-Ru(Cu) core-shell electrocatalysts for polymer electrolyte fuel cells

Pt(Cu)/C and Pt-Ru(Cu)/C electrocatalysts with core-shell structure supported on Vulcan Carbon XC72R have been synthesized by potentiostatic deposition of Cu nanoparticles on the support, galvanic exchange with Pt and spontaneous deposition of Ru species. The duration of the electrodeposition time of the different species has been modified and the obtained electrocatalysts have been characterized using electrochemical and structural techniques. The High Resolution Transmission Electron Microscopy (HRTEM), Fast Fourier Transform (FFT) and Energy Dispersive X-ray (EDX) microanalyses allowed the determining of the effects of the electrodeposition time on the nanoparticle size and composition. The best conditions identified from Cyclic Voltammetry (CV) corresponded to onset potentials for CO and methanol oxidation on Pt-Ru(Cu)/C of 0.41 and 0.32 V vs. the Reversible Hydrogen Electrode (RHE), respectively, which were smaller by about 0.05 V than those determined for Ru-decorated commercial Pt/C. The CO oxidation peak potentials were about 0.1 V smaller when compared to commercial Pt/C and Pt-Ru/C. The positive effect of Cu was related to its electronic effect on the Pt shells and also to the generation of new active sites for CO oxidation. The synthesis conditions to obtain the best performance for CO and methanol oxidation on the core-shell Pt-Ru(Cu)/C electrocatalysts were identified. When compared to previous results in literature for methanol, ethanol and formic acid oxidation on Pt(Cu)/C catalysts, the present results suggest an additional positive effect of the deposited Ru species due to the introduction of the bifunctional mechanism for CO oxidatio

Removal of 4-hydroxyphenylacetic acid from aqueous medium by electrochemical oxidation with a BDD anode: mineralization, kinetics and oxidation products

The degradation of 100 mL of solutions containing 4-hydroxyphenylacetic acid in 0.050 M Na2SO4 at pH 3.0 has been performed by anodic oxidation with electrogenerated H2O2 (AO-H2O2) using a stirred tank reactor equipped with a boron-doped diamond (BDD) anode and an air-diffusion cathode. An almost total mineralization with 95.5% total organic carbon (TOC) removal was achieved for a 1.03 mM substrate solution at 100 mA cm-2. The effect of current density between 16.7 and 100 mA cm-2 and 4-hydroxyphenylacetic acid content between 0.21 and 2.06 mM was examined. Greater current efficiency with lower specific energy consumption and smaller mineralization was found at low current density and high substrate concentration. The TOC abatement as well as the 4-hydroxyphenylacetic acid concentration decay obeyed a pseudo-first-order kinetics. The oxidation role of hydroxyl radical formed from water discharge at the BDD anode is explained on the basis of its electrogeneration rate and competitive wasting reactions. 4-Hydroxybenzenemethanol and its derivative 4-hydroxybenzenealdehyde were identified as primary aromatic by-products by gas chromatography-mass spectrometry. Ion-exclusion HPLC allowed the detection of low amounts of the persistent oxalic acid during the AO-H2O2 process. The remaining TOC in final electrolyzed solutions is related to the presence of a large proportion of unidentified by-products that are even more recalcitrant than common short-linear aliphatic carboxylic acids

Treatment of olive oil mill wastewater by single electrocoagulationwith different electrodes and sequentialelectrocoagulation/electrochemical Fenton-based processes

The treatment of olive oil mill wastewater (OOMW) by novel sequential processes involving electrocoagulation (EC) followed by electro-Fenton (EF) or photoelectro-Fenton (PEF) under UVA irradiation has been studied using a boron-doped diamond anode and an air-diffusion cathode for H2O2 electrogeneration. Their performance was monitored from the removal of total organic carbon (TOC), chemical oxygen demand, turbidity, total solids and total nitrogen, as well as from the energy consumption. Preliminary EC assays were performed with one pair of electrodes made of Al, Fe, AISI 304 or AISI 316L. The Fe/Fe cell showed the best performance, yielding 40% TOC decay in 20 min. Subsequent EF or PEF at natural pH 7.2 performed similarly, whereas PEF became superior at pH 3.0 due to the action of UVA photons. Comparison between EC/PEF and single EF or PEF at pH 3.0 and 25 mA cm-2 with 0.50 mM Fe2+ revealed the positive outcome of the sequential process, attaining 97.1% TOC abatement after 600 min. GC-MS analysis of the raw wastewater allowed identifying 18 cyclic and 27 aliphatic compounds, most of which could not be removed by EC. The final solutions in EC/EF and EC/PEF contained a large plethora of persistent long-chain aliphatic acids and alkanes

4-Hydroxyphenylacetic acid oxidation in sulfate and real olive oil mill wastewater by electrochemical advanced processes with a boron-doped diamond anode

The degradation of 4-hydroxyphenylacetic acid, a ubiquitous component of olive oil mill wastewater (OOMW), has been studied by anodic oxidation with electrogenerated H2O2 (AO-H2O2), electro-Fenton (EF) and photoelectro-Fenton (PEF). Experiments were performed in either a 0.050 M Na2SO4 solution or in real OOMW at pH 3.0, using a cell with a boron-doped diamond (BDD) anode and an air-diffusion cathode for H2O2 generation. Hydroxyl radicals formed at the BDD surface from water oxidation in all processes and/or in the bulk from Fenton's reaction between added Fe2+ and generated H2O2 in EF and PEF were the main oxidants. In both matrices, the oxidation ability of the processes increased in the order AO-H2O2 < EF < PEF. The superiority of PEF was due to the photolytic action of UVA radiation on photosensitive by-products, as deduced from the quick removal of Fe(III)-oxalate complexes. The effect of current density and organic content on the performance of all treatments was examined. 4-Hydroxyphenylacetic acid decay obeyed a pseudo-first-order kinetics. The PEF treatment of 1.03 mM 4-hydroxyphenylacetic acid in 0.050 M Na2SO4 allowed 98% mineralization at 360 min even at low current density, whereas 80% mineralization and a significant enhancement of biodegradability were achieved with the real OOMW

Degradation of trans-ferulic acid in acidic aqueous medium by anodic oxidation, electro-Fenton and photoelectro-Fenton

Solutions of pH 3.0 containing trans-ferulic acid, a phenolic compound in olive oil mill wastewater, have been comparatively degraded by anodic oxidation with electrogenerated H2O2 (AO-H2O2), electro-Fenton (EF) and photoelectro-Fenton (PEF). Trials were performed with a BDD/air-diffusion cell, where oxidizing ¿OH was produced from water discharge at the BDD anode and/or in the solution bulk from Fenton's reaction between cathodically generated H2O2 and added catalytic Fe2+. The substrate was very slowly removed by AO-H2O2, whereas it was very rapidly abated by EF and PEF, at similar rate in both cases, due to its fast reaction with ¿OH in the bulk. The AO-H2O2 process yielded a slightly lower mineralization than EF, which promoted the accumulation of barely oxidizable products like Fe(III) complexes. In contrast, the fast photolysis of these latter species under irradiation with UVA light in PEF led to an almost total mineralization with 98% total organic carbon decay. The effect of current density and substrate concentration on the performance of all treatments was examined. Several solar PEF (SPEF) trials showed its viability for the treatment of wastewater containing trans-ferulic acid at larger scale. Four primary aromatic products were identified by GC-MS analysis of electrolyzed solutions, and final carboxylic acids like fumaric, acetic and oxalic were detected by ion-exclusion HPLC. A reaction sequence for trans-ferulic acid mineralization involving all the detected products is finally proposed

Electrochemical destruction of trans-cinnamic acid by advanced oxidation processes: kinetics, mineralization, and degradation route

Acidic solutions of trans-cinnamic acid at pH 3.0 have been comparatively treated by anodic oxidation with electrogenerated H2O2 (AO-H2O2), electro-Fenton (EF) and photoelectro-Fenton (PEF). The electrolytic experiments were carried out with a boron-doped diamond (BDD)/air-diffusion cell. The substrate was very slowly abated by AO-H2O2 because of its low reaction rate with oxidizing ¿OH produced from water discharge at the BDD anode. In contrast, its removal was very rapid and at similar rate by EF and PEF due to the additional oxidation by ¿OH in the bulk, formed from Fenton's reaction between cathodically generated H2O2 and added Fe2+. The AO-H2O2 treatment yielded the lowest mineralization. The EF process led to persistent final products like Fe(III) complexes, which were quickly photolyzed upon UVA irradiation in PEF to give an almost total mineralization with 98% total organic carbon removal. The effect of current density and substrate concentration on all the mineralization processes was examined. GC-MS analysis of electrolyzed solutions allowed identifying five primary aromatics and one heteroaromatic molecule, whereas final carboxylic acids like fumaric, acetic and oxalic were quantified by ion-exclusion HPLC. From all the products detected, a degradation route for trans-cinnamic acid is proposed

El paper dels sistemes de gestió en el desenvolupament de competències transversals en els estudiants

S’ha treballat la formació competencial dels estudiants mitjançant la realització d’activitats relacionades amb la implementació de sistemes de gestió (qualitat, medi ambient i seguretat). A l’assignatura “Qualitat i Prevenció” (Grau Química), els alumnes han fet auditories de medi ambient i seguretat als laboratoris de pràctiques de la Facultat de Química. Els alumnes de l’assignatura “Direcció d’operacions en el sector químic” (màster Enginyeria Química) han treballat la implementació del sistemes de gestió mitjançant un joc de rol. Finalment, a “Anàlisi i estimació del risc” (màster Enginyeria Química) s’ha treballat una part concreta del sistema de gestió de la seguretat mitjançant l’anàlisi de risc d’una pràctica de laboratori. Els estudiants han treballat competències relacionades amb l’ètica, capacitat d’expressió oral i escrita, capacitat de diàleg, capacitat de lideratge, gestió de la qualitat, el medi ambient i la seguretat. Els resultats de les actuacions han posat de manifest mancances i problemes als laboratoris i als sistemes de gestió, l’anàlisi del quals ha de permetre millorar la qualitat de les pràctiques i dels ensenyaments. Finalment, les enquestes fetes a alguns dels grups implicats han reflectit un alt grau de satisfacció amb la feina feta i la manera de fer-la

Les competències transversals i les auditories als laboratoris de pràctiques de la Facultat de Química: desenvolupament i anàlisi

S’ha treballat la formació competencial dels estudiants mitjançant la realització d’auditories del sistema de gestió de la qualitat dels laboratoris de practiques de la Facultat de Química. Per fer aquesta tasca, s’ha seleccionat com auditors a 102 estudiants de l’assignatura “Qualitat i Prevenció” del Grau de Química, els quals, després d’una breu formació, han actuat com auditors en 49 auditories, la qual cosa ha implicat també la participació de 99 estudiants i 49 professors com a interlocutors en els laboratoris auditats. En total han estat auditats 49 torns de pràctiques relacionats amb els diferents tipus d’assignatures pràctiques impartides per tots els departaments de la Facultat i corresponents als tres graus que s’imparteixen (Química, Enginyeria Química i Enginyeria de Materials), havent estat auditats pràcticament tots els laboratoris docents de la Facultat. Seguint els objectius del projecte, els estudiants han pogut treballar competències transversals relacionades amb l’ètica, la capacitat d’expressió oral i escrita, la capacitat de diàleg, la capacitat de lideratge, l’anàlisi i la interpretació de dades, la gestió de la qualitat, el treball respectuós amb el medi ambient, la seguretat, etc. Per tant, aquest projecte ha sigut una eina important en la seva formació. D’altra banda, dels resultats dels informes d’auditoria realitzats pels estudiants, s’han posat de manifest una sèrie de mancances i problemes als laboratoris que estan sent analitzats per tal de millorar la qualitat de les pràctiques. Finalment, s’han realitzat enquestes de satisfacció a tots els grups implicats (estudiants auditors, estudiants auditats, professors auditats) i els resultats de les mateixes han posat de manifest un alt grau de satisfacció amb la feina feta i la manera de fer-la.PMI

The surveys to the companies: a tool for the improvement of degrees

In scientific and technical degrees, the opinion of the final employers on the given subjects is really important. For this reason, the Quality Committee (CQ) of the Faculty of Chemistry of the University of Barcelona prepared a survey for chemical, engineering and pharmaceutical companies asking about the academic training required by the companies. The survey consists of nine sections including items related to laboratory operations, chemical processes, calculation methods, management systems (quality, environment and safety) or general management information. In addition, at the end of each section, a question inquires the companies about the competences shown by students in the items of the section. The results were compared with that of a similar survey carried out in 2007. The scores obtained, between 2 and 3, for all the items (score: 1, not important; 2, unimportant; 3, important; 4, very important), show that companies accept the training given to our students and the competences achieved by them. However, according to their opinion, it is possible to improve this training, especially in the subjects related to management (time, information, environment, quality, safety, etc.). Therefore, surveys are a good tool for the evaluation of the training achieved in our degrees and, consequently, for improving degrees and the teaching task, according the Quality Management System implemented in the Faculty of Chemistry