0000000000026364
AUTHOR
Rita Sánchez-tovar
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 atmosphere on photoelectrochemical response of TiO2 nanotubes anodized under controlled hydrodynamic conditions
[EN] The influence of three annealing atmospheres (air, nitrogen and argon) and the use of controlled hydrodynamic conditions (from 0 to 5000 rpm) on morphological, structural, chemical and photoelectrochemical properties of TiO2 nanotubes have been evaluated. For this purpose, different characterization techniques have been used: Field Emission Scanning Electron Microscopy, Raman Confocal Laser Spectroscopy, X-Ray Diffraction, X-Ray Photoelectron Spectroscopy, Incident Photon-to-electron Conversion Efficiency measurements, ultraviolet-visible absorption spectra, Mott-Schottky analysis and photoelectrochemical water splitting tests. According to the results, it can be concluded that both hy…
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…
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…
Degradation of Diazinon based on photoelectrocatalytic technique using enhanced WO3 nanostructures: Mechanism and pathway
[EN] In this work, a resistant and toxic pesticide called diazinon was degraded through the photoelectrocatalysis (PEC) technique using tungsten oxide (WO3) nanostructures, applying an external bias of 1VAg/AgCl and simulated solar illumination. For this, WO3 nanostructures have been synthesized using electrochemical anodization in 0.05 M hydrogen peroxide and 1.5 M of different acidic electrolytes: H2SO4, CH4O3S or HNO3. Morphology, composition and crystallinity of the samples were evaluated through Field Emission Scanning Electron Microscopy (FE-SEM), Atomic Force Microscopy (AFM) and Raman Spectroscopy. Then, the photoelectrochemical properties of the samples were analyzed by Photo-Elect…
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…
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…
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.
Original Approach to Synthesize TiO2/ZnO Hybrid Nanosponges Used as Photoanodes for Photoelectrochemical Applications
[EN] In the present work, TiO2/ZnO hybrid nanosponges have been synthesized for the first time. First, TiO2 nanosponges were obtained by anodization under hydrodynamic conditions in a glycerol/water/NH4F electrolyte. Next, in order to achieve the anatase phase of TiO2 and improve its photocatalytic behaviour, the samples were annealed at 450 degrees C for 1 h. Once the TiO2 nanosponges were synthesized, TiO2/ZnO hybrid nanosponges were obtained by electrodeposition of ZnO on TiO2 nanosponges using different temperatures, times, and concentrations of zinc nitrate (Zn(NO3)(2)). TiO2/ZnO hybrid nanosponges were used as photoanodes in photoelectrochemical water splitting tests. The results indi…
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 …
Synthesis of WO3 nanorods through anodization in the presence of citric acid: Formation mechanism, properties and photoelectrocatalytic performance
[EN] In this study, WO3 nanomds have been fabricated by simple anodization in the presence of different amounts of citric acid and at different anodization times. A comprehensive morphological, structural, electrochemical and photoelectrochemical characterization of different samples has been carried out. Moreover, a formation mechanism for WO3 nanorods has been proposed. Finally, these nanostructures have been proven to be excellent visible-light photoelectrocatalysts to remove persistent organic pollutants present in wastewaters, such as fenamiphos. Almost the 80% of this molecule was eliminated from the test solution after 180 min of irradiation, indicating the great potential of these W…
Implementación del método del caso en la asignatura de Ingeniería de Procesos y Productos II del grado en Ingeniería Química
[EN] In this work, the case method has been used in the subject Process and Product Engineering II, which belongs to the fourth course of the Chemical Engineering Degree of the Universitat de València. Different cases have been proposed in the classroom practices in order to students acquire the competences of the subject and improve the results of the exam. A rubric was designed to evaluate the cases which was accessible to the students. The cases were proposed in the exam, in particular, cases related to four lessons which are usually complicated to students and the results obtained for these cases were compared with the results obtained in the questions (presented in a theoretical way) o…
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…
Control on the morphology and photoelectrocatalytic properties of ZnO nanostructures by simple anodization varying electrolyte composition
Abstract Zinc oxide nanostructured electrodes were successfully synthesized by a simple method of anodization in different aqueous bicarbonate electrolytes. The influence of the anodization electrolyte composition (by adding ethanol or glycerol) on the morphology and the photoelectrocatalytic properties of the zinc oxide electrodes was studied, as well as the combined effect of anodizing under controlled hydrodynamic conditions. Field Emission Scanning Electron Microscope (FE-SEM) images of the ZnO electrodes showed that the addition of ethanol or glycerol to the anodization electrolyte resulted in changes in size and morphology of the nanostructures. Thus, ZnO nanowires, nanotubes, nanospo…
Novel TiO2-WO3 self-ordered nanotubes used as photoanodes: Influence of Na2WO4 and H2O2 concentration during electrodeposition
[EN] Hybrid TiO2-WO3 nanostructures has been synthesized by electrochemical anodization under controlled hydrodynamic conditions followed by electrodeposition in the presence of different contents of Na2WO4 (5, 15 and 25 mM) and H2O2 (20, 30 and 40 mM). The influence of the electrolyte used for electrodeposition on the morphology, crystalline structure and photoelectrochemical response for water splitting has been evaluated through Field Emission Electronic Microscopy, High-Resolution Transmission Electron Microscopy, Confocal Raman Spectroscopy, Grazing Incidence X Ray Diffraction, X-Ray Photoelectron Spectroscopy, Atomic Force microscopy and photocurrent versus potential measurements. Add…
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…