0000000000026365
AUTHOR
R.m. Fernández-domene
ZnO/ZnS heterostructures for hydrogen production by photoelectrochemical water splitting
This work studies the photoelectrochemical behavior of novel ZnO/ZnS heterostructures obtained by means of anodization in water and glycerol/water/NH4F electrolytes with different Na2S additions under controlled hydrodynamic conditions. For this purpose different techniques such as Field Emission Scanning Electronic Microscopy (FE-SEM) with EDX, Raman spectroscopy and photoelectrochemical water splitting tests under standard AM 1.5 conditions have been carried out. The obtained results showed that the hydrodynamic conditions promoted an ordered nanotubular morphology which facilitates electron-hole separation and consequently, the photoelectrochemical activity for water splitting is enhance…
Influence of annealing conditions on the photoelectrocatalytic performance of WO3 nanostructures
[EN] Nanostructured WO3 photoanodes have been synthesized by electrochemical anodization under controlled hydrodynamic conditions in acidic media in the presence of 0.05 M H2O2. Subsequently, samples have been subjected to a thermal treatment (annealing) at different temperatures (400 degrees C, 500 degrees C and 600 degrees C) and under different gaseous atmospheres (air, N-2, Ar). The influence of these annealing conditions on the morphology, crystallinity, photoelectrochemical behavior and dopant chemistry of the different photoanodes has been investigated through Electronic Microscopy, Raman Spectroscopy, Photoelectrochemical Impedance Spectroscopy and Mott-Schottky analysis. In general…
Thermogalvanic corrosion of Alloy 31 in different heavy brine LiBr solutions
Thermogalvanic corrosion generated between two electrodes of Alloy 31, a highly-alloyed austenitic stainless steel (UNS N08031), has been investigated imposing different temperature gradients in three deaerated LiBr solutions, under open circuit conditions by using a zero-resistance ammeter (ZRA). Besides EIS spectra were acquired in order to explain the obtained results. On the whole, cold Alloy 31 electrodes were anodic to hot Alloy 31 electrodes, since an increase in temperature favoured the cathodic behaviour of the hot electrode. Thermogalvanic corrosion of Alloy 31 in the LiBr solutions studied was not severe, although it negatively affects the corrosion resistance of the cold anode. …
Visible-light photoelectrodegradation of diuron on WO3 nanostructures
[EN] The degradation of pesticide diuron has been explored by photoelectrocatalysis (PEC) under visible light illumination using two different WO3 nanostructures, obtained by anodization of tungsten. The highest degradation efficiency (73%) was obtained for WO3 nanosheets synthesized in the presence of small amounts of hydrogen peroxide (0.05 M). For that nanostructure, the kinetic coefficient for diuron degradation was 133% higher than that for the other nanostructure (anodized in the presence of fluoride anions). These results have been explained by taking into account the different architecture and dimensions of the two WO3 nanostructures under study.
Effect of Reynolds number and lithium cation insertion on titanium anodization
This work studies the influence of using hydrodynamic conditions (Reynolds number, Re = 0 to Re = 600) during Ti anodization and Li+ intercalation on anatase TiO2 nanotubes. The synthesized photocatalysts were characterized by using Field Emission Scanning Electron Microscope (FE-SEM), Raman Confocal Laser Microscopy, Electrochemical Impedance Spectroscopy (EIS), Mott-Schottky analysis (M-S), photoelectrochemical hydrogen production and resistance to photocorrosion tests. The obtained results showed that the conductivity of the NTs increases with Li+ intercalation and Re. The latter is due to the fact that the hydrodynamic conditions eliminate part of the initiation layer formed over the tu…
Customized WO3 nanoplatelets as visible-light photoelectrocatalyst for the degradation of a recalcitrant model organic compound (methyl orange)
[EN] WO3 nanoplatelets have been synthesized by electrochemical anodization in acidic electrolytes containing two different complexing agents: fluorides and hydrogen peroxide. The influence of the morphology and size of these nanoplatelets on their photoelectrocatalytic performance has been studied following the degradation of a model organic recalcitrant compound, such as methyl orange (MO). The effect of several supporting electrolytes on this photodegradation process has also been checked. The best MO decoloration was observed for nanoplatelets fabricated in the presence of low H2O2 concentrations, whose distribution and small size made them expose a very high surface area to the problem…
Elimination of pesticide atrazine by photoelectrocatalysis using a photoanode based on WO3 nanosheets
[EN] The photoelectrocatalytic (PEC) degradation of a persistent and toxic herbicide, atrazine, has been investigated by using a novel and high-performance WO3 nanostructure in the form of nanosheets/nanorods as photoanode. The nanostructure has been synthesized by anodization in acidic media in the presence of a very small amount (0.05 M) of H2O2, and its morphology, as well as its electrochemical and photoelectrochemical properties have been characterized. Atrazine was completely degraded after similar to 180 min of reaction following pseudo-first order kinetics, and 2-hydroxyatrazine was identified as the main intermediate species. Moreover, the s-triazine ring in cyanuric acid (the fina…
Passivity Breakdown of Titanium in LiBr Solutions
The passive behavior of titanium and its susceptibility to undergo localized attack in different LiBr solutions at 25 degrees C have been investigated using different electrochemical techniques: potentiodynamic polarization curves, potentiostatic passivation tests, EIS measurements and Mott-Schottky analysis. In low and moderately concentrated LiBr solutions, the breakdown potential E-b decreased with increasing bromide concentrations, while in highly concentrated LiBr solutions, E-b increased with increasing LiBr concentration. In the most concentrated LiBr solution (11.42M) Ti did not undergo passivity breakdown even at 9 V-Ag/AgCl. This observation can be explained by a a decrease in the…
Improvement of the electrochemical behaviour of Zn-electroplated steel using regenerated Cr(III) passivation baths
[EN] Conversion coatings based on trivalent chromium are more sensitive to the presence of zinc and iron impurities than the chromate formulations. This fact contributes to a decrease in the quality of passivation and to the generation of a significant amount of hazardous liquid waste. Recently, a new eco-innovative process based on Emulsion Pertraction Technology (EPT) is being implemented at industrial scale for selectively removing Zn and Fe from spent passivation baths in order to enhance the lifetime of the Cr (III) baths. In this study, the effect of Zn and Fe removal on the electrochemical behaviour of Zn-electroplated steel samples was evaluated by means of polarisation curves and e…
Cathodoluminescence characterization of ZnO/ZnS nanostructures anodized under hydrodynamic conditions
[EN] ZnO/ZnS nanostructures were successfully synthesized by a simple electrochemical anodization of zinc in a glycerol based electrolyte containing sulfide-ammonium fluoride. The influence of different hydrodynamic conditions and anodization potentials during anodization on the morphological and electronic properties of the obtained ZnO/ZnS nanostructures was studied. The anodized samples were characterized using confocal Raman microscopy, X-Ray Diffraction (XRD), Field Emission Scanning Electronic Microscopy (FE-SEM), cathodoluminescence (CL), and photoelectrochemical water splitting tests under standard AM 1.5 conditions. The results showed that hydrodynamic conditions and higher potenti…
Photoelectrocatalyzed degradation of organophosphorus pesticide fenamiphos using WO3 nanorods as photoanode
[EN] In this study, WO3 nanostructures were synthesized by the electrochemical anodization technique to use them on the degradation of persistent organic compounds such as the pesticide fenamiphos. The acids electrolyte used during the anodization were two different: 1.5 M H2SO4-0.05 M H2O2 and 1.5 M CH4O3S-0.05 M H2O2. Once the samples have been manufactured, they have been subjected to different tests to analyze the properties of the nanostructures. With Field Emission Scanning Electron Microscopy (FESEM) the samples have been examined morphologically, their composition and crystallinity has been studied through Raman Spectroscopy and their photoelectrochemical behaviour by Photoelectroch…
Study of Passive Films Formed on AISI 316L Stainless Steel in Non-Polluted and Underwater-Volcano-Polluted Seawater
This work studies the semiconducting behavior of passive films formed on AISI 316L (UNS S31603) in two different sea-water solutions, non-polluted and polluted, collected from the volcano of El Hierro Island. Polarization measurements, potentiostatic passivation tests, electrochemical impedance spectroscopy, and capacitance measurements were performed. Results show that the polluted seawater worsens passivation kinetics. Additionally, passive films formed on AISI 316L stainless steel in polluted seawater have been found to be less protective than those formed in non-polluted seawater, showing a more defective structure, owing to the acidity of the polluted medium.
Synergistic effect between hydrodynamic conditions during Ti anodization and acidic treatment on the photoelectric properties of TiO2 nanotubes
In the present work, the combined influence of controlled hydrodynamic conditions during Ti anodization and the acidic treatment with HClO4 on the photoelectric properties of mixed anatase/rutile TiO2 nanotubes has been studied. Anodized samples were analyzed by means of Field Emission Scanning Electronic Microscopy (FE-SEM), Confocal Raman Microscopy, electrochemical measurements (electrochemical impedance spectroscopy and Mott-Schottky analysis) and photoelectrochemical measurements. It has been observed that the use of hydrodynamic conditions increases the surface area of nanotubes, while acidic treatment enhances their conductivity. Besides, there is a clear synergistic effect between t…
Effect of alloying elements on the electronic properties of thin passive films formed on carbon steel, ferritic and austenitic stainless steels in a highly concentrated LiBr solution
The influence of alloying elements on the electrochemical and semiconducting properties of thin passive films formed on several steels (carbon steel, ferritic and austenitic stainless steels) has been studied in a highly concentrated lithium bromide (LiBr) solution at 25 °C, by means of potentiodynamic tests and Mott Schottky analysis. The addition of Cr to carbon steel promoted the formation of a p-type semiconducting region in the passive film. A high Ni contentmodified the electronic behaviour of highly alloyed austenitic stainless steels.Mo did notmodify the electronic structure of the passive films, but reduced the concentration of defects.
Repassivation of the damage generated by cavitation on UNS N08031 in a LiBr solution by means of electrochemical techniques and Confocal Laser Scanning Microscopy
Abstract The objective of this work is to study the influence of cavitation on the corrosion behaviour of Alloy 31, a highly-alloyed austenitic stainless steel (UNS N08031), in a LiBr heavy brine solution (992 g/L) at 25 °C. The presence of cavitation shifted the OCP value towards the active direction by 708 mVAg/AgCl, increased anodic current densities and passivation current density, ip, and reduced the pitting potential, Ep. Repassivation behaviour of Alloy 31 has been investigated by using potentiostatic tests at different potentials. The current density transient obtained after interrupting cavitation was used to obtain the repassivation index, n, provided by the slope of the log i(t) …
Influence of electrolyte temperature on the synthesis of iron oxide nanostructures by electrochemical anodization for water splitting
[EN] Iron oxide nanostructures are an attractive option for being used as photocatalyst in photoelectrochemical applications such as water splitting for hydrogen production. Nanostructures can be obtained by different techniques, and electrochemical anodization is one of the simplest methods which allows high control of the obtained morphology by controlling its different operational parameters. In the present study, the influence of the electrolyte temperature during electrochemical anodization under stagnant and hydrodynamic conditions was evaluated. Temperature considerably affected the morphology of the obtained nanostructures and their photoelectrochemical behavior. Several techniques …
Effect of Reynolds number on TiO2 nanosponges doped with Li+ cations
[EN] Anatase TiO2 nanosponges have been synthesized by anodization of Ti, and Li+ cations have been inserted in these nanostructures. The influence of hydrodynamic conditions (Reynolds number, Re = 0 to Re = 600) during anodization has been studied. Li-Doped TiO2 nanosponges were characterized by field emission scanning electron microscopy (FE-SEM), Raman confocal microscopy, electrochemical impedance spectroscopy (EIS) and Mott¿Schottky analysis (M¿S). The photoelectrochemical performance and resistance to photocorrosion were also measured. Li¿TiO2 nanosponges proved to be better photocatalysts for water splitting than Li¿TiO2 nanotubes. Moreover, the photoelectrochemical behavior of the L…
A simple method to fabricate high-performance nanostructured WO3 photocatalysts with adjusted morphology in the presence of complexing agents
[EN] The rich and complex chemistry of tungsten was employed to synthesize innovative WO3 nanoplatelets/nanosheets by simple anodization in acidic electrolytes containing different concentrations of complexing agents or ligands, namely F- and H2O2. The morphological and photoelectrochemical properties of these nanostructures were characterized. The best of these nanostructures generated stable photocurrent densities of ca. 1.8 mA cm(-2) at relatively low bias potentials (for WO3) of 0.7 V-Ag/AgCl under simulated solar irradiation, which can be attributed to a very high active surface area. This work demonstrates that the morphology and dimensions of these nanostructures, as well as their ph…
Photoelectrocatalyzed degradation of a pesticides mixture solution (chlorfenvinphos and bromacil) by WO3 nanosheets
[EN] A photoelectrocatalyst consisting of WO3 nanosheets or nanorods has been synthesized by electrochemical anodization under hydrodynamic conditions, and has been used for the degradation of two toxic pesticides: chlorfenvinphos and bromacil. Nanostructures have been characterized by FESEM and Raman spectroscopy. Photoelectrochemical degradation tests have been carried out both for individual pesticide solutions and for a mixture solution, and the concentration evolution with time has been followed by UV¿Vis spectrophotometry. For individual pesticides, pseudo-first order kinetic coefficients of 0.402 h¿1 and 0.324 h¿1 have been obtained for chlorfenvinphos and bromacil, respectively, whi…
Electrochemical formation of novel TiO2-ZnO hybrid nanostructures for photoelectrochemical water splitting applications
[EN] In this study, hybrid ZnO-TiO2 nanostructures have been synthesised by means of a simple electrochemical anodisation of titanium and subsequently ZnO electrodeposition. The influence of Zn(NO3)(2) concentration and temperature during the electrodeposition process was evaluated. Different techniques were used to analyse the synthesised nanostructures, notably Field Emission Scanning Electron Microscopy (FE-SEM) with Energy-dispersive X-ray spectroscopy (EDX) and Confocal Microscopy with Raman spectroscopy coupled with an Atomic Force Microscope. Photoelectrochemical water splitting tests were also performed at the hybrid nanostructures. According to the results, the photoelectrochemical…
Controlled hydrodynamic conditions on the formation of iron oxide nanostructures synthesized by electrochemical anodization: Effect of the electrode rotation speed
[EN] Iron oxide nanostructures are of particular interest because they can be used as photocatalysts in water splitting due to their advantageous properties. Electrochemical anodization is one of the best techniques to synthesize nanostructures directly on the metal substrate (direct back contact). In the present study, a novel methodology consisting of the anodization of iron under hydrodynamic conditions is carried out in order to obtain mainly hematite (alpha-Fe2O3) nanostructures to be used as photocatalysts for photoelectrochemical water splitting applications. Different rotation speeds were studied with the aim of evaluating the obtained nanostructures and determining the most attract…
Formation of ZnO nanowires by anodization under hydrodynamic conditions for photoelectrochemical water splitting
[EN] The present work studies the influence of hydrodynamic conditions (from 0 to 5000 rpm) during Zn anodization process on the morphology, structure and photoelectrocatalytic behavior of ZnO nanostructures. For this purpose, analysis with Confocal Laser-Raman Spectroscopy, Field Emission Scanning Electron Microscope (FE-SEM) and photoelectrochemical water splitting tests were performed. This investigation reveals that hydrodynamic conditions during anodization promoted the formation of ordered ZnO nanowires along the surface that greatly enhance its stability and increases the photocurrent density response for water splitting in a 159% at the 5000 rpm electrode rotation speed.
Investigación en el aula: evaluación de la metodología de aprendizaje basado en problemas en la asignatura de Corrosión
[ES] La metodología de Aprendizaje Basado en Problemas (ABP) se introdujo por primera vez en un curso de Corrosión del Master de Ingeniería Química de la Universitat Politècnica de València, durante el curso 2018-2019. Se diseñaron y presentaron diferentes problemas relacionados con todos estos conceptos como metodología de aprendizaje basado en problemas. Para evaluar el empleo de este tipo de metodología activa se plantea la elaboración de una encuesta a los estudiantes de manera anónima e individual y la realización de una matriz de escenarios presentes y futuros para la asignatura de forma grupal. Es importante señalar que a pesar de que para muchos de los estudiantes (67%) esta era la …
Corrosion behaviour of a highly alloyed austenitic alloy UB6 in contaminated phosphoric acid
The influence of temperature (20–80°C) on the electrochemical behaviour of passive films anodically formed on UB6 stainless steel in phosphoric acid solution (5.5 M H3PO4) has been examined by using potentiodynamic curves, electrochemical impedance spectroscopy, and Mott-Schottky analysis. UB6 stainless steel in contaminated phosphoric acid is characterised by high interfacial impedance, thereby, illustrating its high corrosion resistance. The obtained results show that the films behave as n-type and p-type semiconductors in the potential range above and below the flat band potential, respectively. This behaviour is assumed to be the consequence of the semiconducting properties of the iron …
Study of the annealing conditions and photoelectrochemical characterization of a new iron oxide bi-layered nanostructure for water splitting
Iron oxide nanostructures have emerged as promising materials for being used as photocatalysts for hydrogen production due to their advantageous properties. However, their low carrier mobility and short hole diffusion length limit their efficiency in water splitting. To overcome these drawbacks, in the present study, we synthetized a new hematite (alpha-Fe2O3) bi-layered nanostructure consisting of a top nanosphere layer and a nanotubular underneath one by electrochemical anodization. Annealing parameters such as temperature, heating rate and atmosphere were studied in detail in order to determine the optimum annealing conditions for the synthetized nanostructure. The obtained new bi-layere…
Cavitation corrosion and repassivation kinetics of titanium in a heavy brine LiBr solution evaluated by using electrochemical techniques and Confocal Laser Scanning Microscopy
The cavitation corrosion behaviour of commercially pure Grade 2 titanium in a 992 g/l LiBr solution has been investigated at 25 °C using an ultrasound device. Cavitation was found to have more influence on the anodic branch than on the cathodic branch, shifting the corrosion potential, Ecorr, and the OCP value towards more negative potentials, and increasing the corrosion current density, icorr, by six times. The repassivation kinetics of Grade 2 titanium have also been studied in the 992 g/l LiBr solution, at 25 °C and various applied potentials, using cavitation to damage the electrode surface. The repassivation kinetics have been analysed in terms of the current density flowing from the …
TiO2 Nanostructures for Photoelectrocatalytic Degradation of Acetaminophen
[EN] Advanced oxidation processes driven by renewable energy sources are gaining attention in degrading organic pollutants in waste waters in an efficient and sustainable way. The present work is focused on a study of TiO2 nanotubes as photocatalysts for photoelectrocatalytic (PEC) degradation of acetaminophen (AMP) at different pH (3, 7, and 9). In particular, different TiO2 photocatalysts were synthetized by stirring the electrode at different Reynolds numbers (Res) during electrochemical anodization. The morphology of the photocatalysts and their crystalline structure were evaluated by field emission scanning electron microscopy (FESEM) and Raman confocal laser microscopy (RCLM). These a…
Photoelectrochemical removal of chlorfenvinphos by using WO3 nanorods: Influence of annealing temperature and operation pH
[EN] A visible-light driven photoelectrochemical degradation process has been applied to a solution polluted with the organophosphate insecticide chlorfenvinphos. Different WO3 nanosheets/nanorods have been used as photoanodes. These nanostructured electrodes have been fabricated by anodization of tungsten and, subsequently, they have been subjected to a thermal treatment (annealing). The combined influence of annealing temperature (400¿°C and 600¿°C) and operation pH (1 and 3) on the photoelectrocatalytic behavior of these nanorods has been examined through a statistical analysis. Morphological, structural and photoelectrochemical characterizations have also been carried out. The chlorfenv…
Evaluación de las actividades realizadas mediante la metodología de Aprendizaje Basado en Problemas
[ES] La metodología de Aprendizaje Basado en Problemas (ABP) requiere un enfoque de evaluación en el que se evalúen una serie de competencias específicas y transversales. Esta evaluación debe de tener un carácter formativo que permita a los estudiantes identificar y corregir los errores a tiempo. Por lo tanto, es necesario disponer de herramientas para poder evaluar apropiadamente los resultados de aprendizaje y las competencias establecidas. En la asignatura de Corrosión de segundo de Máster de Ingeniería Química, el ABP se ha evaluado a través de un informe a entregar tras cada sesión de ABP, en donde se recogen las principales conclusiones tras la resolución cooperativa del problema plan…
Photoelectrochemical characterization of anatase-rutile mixed TiO2 nanosponges
This work studies the influence of using hydrodynamic conditions during anodization on the morphology and electrochemical properties of anatase/rutile mixed TiO2 nanotubes (Reynolds number, Re = 0) and nanosponges (Re > 0). To this purpose different techniques were used, such as: microscopy techniques (Field-Emission Scanning Electron Microscope, FE-SEM, and Confocal Laser-Raman Spectroscopy), Electrochemical Impedance Spectroscopy (EIS), Mott Schottky (MS) analysis and photoelectrochemical water splitting tests. This investigation demonstrates that the morphology of TiO2 nanostructures may be greatly affected due to the hydrodynamic conditions and it can be adjusted in order to increase th…
Enhancement of photoelectrochemical activity for water splitting by controlling hydrodynamic conditions on titanium anodization
This work studies the electrochemical and photoelectrochemical properties of a new type of TiO2 nanostructure (nanosponge) obtained by means of anodization in a glycerol/water/NH4F electrolyte under controlled hydrodynamic conditions. For this purpose different techniques such as Scanning Electronic Microscopy (SEM), Raman Spectroscopy, Electrochemical Impedance Spectroscopy (EIS) measurements, Mott–Schottky (M−S) analysis and photoelectrochemical water splitting tests under standard AM 1.5 conditions are carried out. The obtained results show that electron–hole separation is facilitated in the TiO2 nanosponge if compared with highly ordered TiO2 nanotube arrays. As a result, nanosponges en…
Green approach to corrosion inhibition of stainless steel in phosphoric acid of Artemesia herba albamedium using plant extract
Essential oil from aerial parts of Artemisia herba-alba from Morocco was hydrodistilled and its chemical composition oil was investigated by capillary GC and GC/MS. The major components were 1,8-cineole (35.6%) and camphor (24.1%). Artemisia herba-alba essential oil AHAO was tested as corrosion inhibitor of stainless steel (SS) in 1M H3PO4 using potentiodynamic polarization (PDP) and electrochemical impedance spectroscopy measurements (EIS) and scanning electronically microscopy (SEM) studies. The results obtained showed that the essential oil of Artemisia reduces the corrosion rate. Tafel polarization method indicates that the plant extract behaves as a mixed type inhibitor. The inhibition…
Novel tree-like WO3 nanoplatelets with very high surface area synthesized by anodization under controlled hydrodynamic conditions
In the present work, a new WO3 nanostructure has been obtained by anodization in a H2SO4/NaF electrolyte under controlled hydrodynamic conditions using a Rotating Disk Electrode (RDE) configuration. Anodized samples were analyzed by means of Field Emission Scanning Electronic Microscopy (FESEM), Confocal Raman Microscopy and photoelectrochemical measurements. The new nanostructure, which consists of nanoplatelets clusters growing in a tree-like manner, presents a very high surface area exposed to the electrolyte, leading to an outstanding enhancement of its photoelectrochemical activity. Obtained results show that the size of nanostructures and the percentage of electrode surface covered by…