Desarrollo y caracterización de electrodos catalíticos basados en polímeros conductores de polipirrol y polianilina sobre diferentes sustratos

Durante los últimos años el desarrollo de tejidos con nuevas propiedades ha sido un campo muy activo. Por ejemplo se han creado tejidos con propiedades termorreguladoras a partir de microcápsulas con materiales que cambian de fase, tejidos autolimpiables, tejidos con acabados hidrófobos, etc. Otro de los campos que se ha estado explorando es el de los tejidos conductores de la electricidad; sobre el cual trata la presente tesis. Se han desarrollado productos basados en tejidos conductores de la electricidad como por ejemplo: un MP3 integrado en una chaqueta, trajes con LEDS, camisetas para monitorizar el estado de los pacientes en los hospitales, etc. Este tipo de modificaciones en los tejidos crea un valor añadido en el producto final además de un creciente mercado que los hace muy interesantes dada la situación actual del sector textil. Se estimó que para el 2008 el campo de los tejidos para monitorizar el estado de los pacientes podía representar un mercado de entre 100 y 1000 millones de dólares. Para la obtención de tejidos conductores de la electricidad, se han empleado tradicionalmente fibras metálicas integradas en los tejidos. El problema que plantean las fibras metálicas es que los movimientos de flexión, torsión y estiramiento que se dan en un tejido acaban por romper las fibras metálicas. Los polímeros conductores se plantean como una alternativa debido a su flexibilidad y su fácil síntesis sobre los tejidos. La polimerización química del pirrol en presencia de sustratos textiles produce una capa uniforme sobre todo el tejido de un espesor menor de 1 um. En el presente trabajo se han obtenido tejidos de poliéster recubiertos con polipirrol/antraquinona sulfonato (AQSA) y polipirrol/fosfotungstato (PW12O40-3)- El empleo de contraiones grandes como son el AQSA (orgánico) y el PW12O40-3 (inorgánico) impediría la salida de los mismos de la estructura (desdopado) del polímero evitando la pérdida de propiedades eléctricas y electroquímicas.Molina Puerto, J. (2011). Desarrollo y caracterización de electrodos catalíticos basados en polímeros conductores de polipirrol y polianilina sobre diferentes sustratos [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/10688Palanci

Scanning electrochemical microscopy for the analysis and patterning of graphene materials: A review

[EN] Graphene and related materials have recently emerged as outstanding materials due to a range of properties such as high mechanical strength, high electron mobility, thermal conductivity, etc. Due to their high surface area and conductivity, graphene materials have also been used for electrochemical applications such as supercapacitors, batteries, sensors, etc. Therefore, the characterization of the electroactivity of graphene materials is necessary and different electrochemical techniques such as cyclic voltammetry and electrochemical impedance spectroscopy have been widely used for this purpose. Scanning electrochemical microscopy has appeared as a unique technique that can be used to test electron transfer kinetics, electroactivity and conductivity of these materials. Even patterns can be created on graphene materials by this technique, This review aims to compile the different works performed with graphene materials and scanning electrochemical microscopy technique and provide new perspectives into the analysis of graphene materials using this technique. (C) 2016 Elsevier B.V. All rights reserved.Authors wish to thank to the Spanish Ministerio de Ciencia e Innovacion (contract MAT2016-77742-C2-1-P) for the financial support. J. Molina is grateful to the Conselleria d'Educacio, Formacio i Ocupacio (Generalitat Valenciana) for the Programa VALi+D Postdoctoral Fellowship (APOSTD/2013/056). Tim Vickers is gratefully acknowledged for help with the English revision.Molina Puerto, J.; Fernández Sáez, J.; Cases Iborra, FJ. (2016). Scanning electrochemical microscopy for the analysis and patterning of graphene materials: A review. Synthetic Metals. 222:145-161. https://doi.org/10.1016/j.synthmet.2016.10.019S14516122

Graphene-based materials for the electrochemical determination of hazardous ions

[EN] The use of graphene in the field of electrochemical sensors is increasing due to two main properties that make graphene and derivatives appealing for this purpose: their conductivity and high surface area. In addition, graphene materials can be easily functionalized with nanoparticles (Au, Pt, etc.) or organic molecules (DNA, polymers, etc.) producing synergies that allow higher sensitivity, lower limit of detection as well as increased selectivity. The present review focuses on the most important works published related to graphene-based electrochemical sensors for the determination of hazardous ions (such as As(III), Cd2+, Pb2+, Hg2+, Cr(VI), Cu2+, Ag+, etc.). The review presents examples of the use of graphene-based electrodes for this purpose as well as important parameters of the sensors such as: limit of detection, linear range, sensitivity, main interferences, stability, and reproducibility. The application of these graphene-based electrodes in real samples (water or food matrices) is indicated, as well. There is room for improvement of these type of sensors and more effort should be devoted to the use of doped graphene (doped for instance with N, B, S, Se, etc.) since electrochemically active sites originated by doping facilitate charge transfer, adsorption and activation of analytes, and fixation of functional moieties/molecules. This will allow the sensitivity and the selectivity of the electrodes to be increased when combined with other materials (nanoparticles/organic molecules). © 2016 Elsevier B.V. All rights reserved.J. Molina and F. Cases wish to thank to the Spanish Ministerio de Ciencia e Innovacion (contract MAT2016-77742-C2-1-P) for the financial support. J. Molina is grateful to the Conselleria d'Educacio, Formacio i Ocupacio (Generalitat Valenciana) for the Programa VALi+D Postdoctoral Fellowship (APOSTD/2013/056). Tim Vickers is gratefully acknowledged for help with the English revision.Molina Puerto, J.; Cases Iborra, FJ.; Moretto, LM. (2016). Graphene-based materials for the electrochemical determination of hazardous ions. Analytica Chimica Acta. 946:9-39. https://doi.org/10.1016/j.aca.2016.10.019S93994

Electrochemical study on an activated carbon cloth modified by cyclic voltammetry with polypyrrole/anthraquinone sulfonate and reduced graphene oxide as electrode for energy storage

[EN] This work describes a two-step procedure for the electrochemical coating of reduced graphene oxide (RGO) and polypyrrole anthraquinone sulfonate (PPyAQS) onto an activated carbon cloth (ACC) by cyclic voltammetry (CV). The textile samples were characterized by CV, electrochemical impedance spectroscopy (EIS) and galvanostatic charge-discharge measurements using a sandwich-type (electrode/separator/electrode) cell designed to operate in three or two-electrode configurations. The presence of RGO onto the ACC surface optimized the electrosynthesis of PPyAQS and reinforced the stability of the polymer with the number of charge/discharge cycles. A retention capacity of 90% after 100 charge-discharge cycles together with an energy density of 7.8¿×¿10¿4¿W¿h¿cm¿2 at a power density of 1.8¿×¿10¿3¿W¿cm¿2 were obtained for the ACC/RGO/PPyAQS sample. The analyses by field emission scanning electron microscopy (FESEM) showed the RGO veils-like and PPyAQS glomerular structures covering the ACC-fibers. The Fourier transform infrared spectroscopy (FTIR) analyses not only detected the presence of PPy and AQS, but also, the changes in the molecular structure of PPyAQS, depending on its oxidation state, as consequence of the redox reactions occurred in the charge/discharge processes in the two-electrode cell.The authors wish to acknowledge to Chemviron Carbon who kindly donated the ZORFLEX® activated carbon fabric. The authors wish to thank the Spanish Agencia Estatal de Investigación de Economía (AEI) and European Union (FEDER funds) for the financial support (contract MAT2016-77742-C2-1-P). Tim Vickers is gratefully acknowledged for help with the English revision. Electron Microscopy Service of the UPV (Universitat Politècnica de València) is gratefully acknowledged for help with FESEM characterization.Fernández Sáez, J.; Bonastre Cano, JA.; Molina Puerto, J.; Cases, F. (2018). Electrochemical study on an activated carbon cloth modified by cyclic voltammetry with polypyrrole/anthraquinone sulfonate and reduced graphene oxide as electrode for energy storage. European Polymer Journal. 103:179-186. https://doi.org/10.1016/j.eurpolymj.2018.04.018S17918610

Characterization of polypyrrole/phosphotungstate membranes by electrochemical impedance spectroscopy

The aim of this study was to design and prepare multifunctional PPy/PW12O403- membranes useful for the development of smart textile fabrics and wastewaters treatments based on the application of electrochemical techniques. These PPy/PW12O403- membranes have been characterized by means of electrochemical impedance spectroscopy by using electrochemical cells with different configurations based on the use of two-, three-, or four-electrode experiments. The activation energy of the films in the temperature range 35-70 degrees C was 170 meV. It has been demonstrated that after measuring the PPy films in different NaCl solutions, both the rate of ionic exchange and the diffusion processes through the membrane are faster for more concentrated solutions. Ionic exchange and diffusion were very prevented with a large cation as tetramethylammonium. The impedance spectra obtained with metal/polymer/electrolyte configuration show that the electrical conduction developed through coatings in strong acid solution is controlled by finite-length diffusion processes with reflective boundary conditions. At pH 13, the electrical response proceeds through the oxide layer (Fe and Cr oxides) and the steel/electrolyte interface. In this case, the polymeric coating is very porous due to the counter-ion disintegration. The decomposition of the counter-ion was corroborated by means of energy dispersive X-ray and Fourier transform infrared spectroscopy. (C) 2013 Elsevier B.V. All rights reserved.Authors thank to the Spanish Ministerio de Ciencia e Innovacion (contract CTM2011-23583) and Universitat Politecnica de Valencia (Primeros Proyectos de Investigacion (PAID-06-10)) for the financial support. J. Molina is grateful to the Conselleria d'Educacio, Formacio i Ocupacio (Generalitat Valenciana) for the Programa VALi+D Postdoctoral Fellowship.Bonastre Cano, JA.; Molina Puerto, J.; Galvan, JC.; Cases Iborra, FJ. (2014). Characterization of polypyrrole/phosphotungstate membranes by electrochemical impedance spectroscopy. Synthetic Metals. 187:37-45. https://doi.org/10.1016/j.synthmet.2013.10.020S374518

Study on the specific capacitance of an activated carbon cloth modified with reduced graphene oxide and polyaniline by cyclic voltammetry

This work describes a two-step process for the electrochemical coating of reduced graphene oxide (RGO) and polyaniline (PANI) onto an activated carbon cloth (ACC) by cyclic voltammetry (CV). The fact that the two syntheses are carried out independently of each other, makes it possible to select the experimental conditions for each one and to study the electrochemical response of RGO, PANI, and PANI onto RGO (RGOPANI), separately. Thus, by modifying the potential limits of the aniline-polymerization reaction, it was possible to observe the influence of RGO and the maximum amount of PANI that the carbon cloth can receive in terms of proper electrochemical response. Electrochemical properties were characterized by CV, galvanostatic charge-discharge curves (using three or two-electrodes symmetric cell configurations) and electrochemical impedance spectroscopy (EIS). A maximum improvement of 25%, 56% and 61% over the initial specific capacitance of ACC (about 129 F g−1) were obtained for RGO, PANI and RGOPANI coatings, respectively. Good cycling stability retaining 83% of the initial capacitance, after 1000 cycles stability test, was obtained for RGOPANI sample. Promising results of energy and power densities were also achieved. In the analyses by Fourier transform infrared spectroscopy (FTIR), the PANI-bands could be clearly identified which is indicative of a significant presence of PANI. Field emission scanning electron microscopy (FESEM) showed the morphology of RGO, PANI and RGOPANI onto the ACC fibers. These analyses helped to explain the electrochemical results.The authors wish to acknowledge to Chemviron Carbon who kindly donated the ZORFLEX (R) activated carbon fabric. The authors wish to thank the Spanish Agenda Estatal de Investigacion (AEI) and European Union (FEDER funds) for the financial support (contract MAT2016-77742-C2-1-P). Tim Vickers is gratefully acknowledged for help with the English revision.Fernández Sáez, J.; Bonastre Cano, JA.; Molina Puerto, J.; Del Río García, AI.; Cases Iborra, FJ. (2017). Study on the specific capacitance of an activated carbon cloth modified with reduced graphene oxide and polyaniline by cyclic voltammetry. European Polymer Journal. 92:194-203. doi:10.1016/j.eurpolymj.2017.04.044S1942039

Chemical, electrical and electrochemical characterization of hybrid organic/inorganic polypyrrole/PW12O403- coating deposited on polyester fabrics

A study of the stability of conducting fabrics of polyester (PES) coated with polypyrrole/PW12O403¿ (organic/inorganic hybrid material) in different pH solutions (1, 7, 13) has been done. Washing tests were also done in views of its possible application in electronic textiles such as antistatic clothing. X-ray photoelectron spectroscopy (XPS) studies have been done to quantify the amount of counter ion that remains in the polymer matrix and determine the doping ratio (N+/N) after the different tests. Scanning electron microscopy (SEM) was also used to observe morphological differences after the different tests. Surface resistivity changes were measured by means of electrochemical impedance spectroscopy (EIS). Scanning electrochemical microscopy (SECM) was employed to measure changes in electroactivity after the different tests. Higher pHs caused a decrease of the doping ratio (N+/N), the loss of part of the counter ions and the decrease of its conducting and electrocatalytic properties. The stability in acid media and neutral media and after the washing test was good. Only at pH 13 the loss of the counter ion was widespread and there was a decrease of its conducting and catalytic properties; although the fabrics continued acting mainly as a conducting material.Authors thank the Spanish Ministerio de Ciencia y Tecnologia, European Union Funds (FEDER) (contract CTM2007-66570-C02-02) and Universitat Politecnica de Valencia (Programa de apoyo a la investigacion y desarrollo de la UPV (PAID-05-08)) for the financial support. J. Molina is grateful to the Conselleria d'Educacio (Generalitat Valenciana) for the FPI fellowship. A.I. del Rio is grateful to the Spanish Ministerio de Ciencia y Tecnologia for the FPI fellowship.Molina Puerto, J.; Fernández Sáez, J.; Del Río García, AI.; Bonastre Cano, JA.; Cases Iborra, FJ. (2011). Chemical, electrical and electrochemical characterization of hybrid organic/inorganic polypyrrole/PW12O403- coating deposited on polyester fabrics. Applied Surface Science. 257:10056-10064. doi:10.1016/j.apsusc.2011.06.140S100561006425

Enteral Feeding: Brain-Visceral Interactions in the Processing of Nutrients

Enteral nutrition is often mandatory, especially for patients in vegetative or minimally conscious state. However, its application is nonviable in certain cases due to various adverse effects. Some of these are explained by absence of the cephalic phase of digestion, during which exocrine, endocrine, and motor physiological responses prepare the digestive system to receive, digest, transform, and utilize ingested nutrients. These responses result from the stimulation by nutrients of cephalic sensory systems, mainly in the oropharyngeal cavity, and can also be elicited by food-related thoughts or expectations. The digestive system appears able to rapidly assess the suitability of food and transmit this information to the brain. The vagus nerve and its brainstem relays in the caudal nucleus of the solitary tract (NST) and parabrachial complex appear to participate in the anatomic pathway responsible for this rapid processing. Thus, blockade of the vagus nerve, NST, or external lateral parabrachial region (LPBe) interrupts expression of conditioned taste preferences induced by administration of “predigested” food, while LPBe activation by electric stimulation generates similar preferences to those observed after cephalic food administration. This review may help design enteral diets better adapted to digestive physiology and develop pharmacological interventions against adverse effects of enteral nutrition

Electrochemical synthesis of polyaniline on conducting fabrics of polyester covered with polypyrrole/PW12O403-. Chemical and electrochemical characterization

Polyaniline (Pani) has been electrochemically polymerized on conducting fabrics of polyester covered with polypyrrole/PW 12O 40 3-, obtaining a double conducting polymer layer. Electrochemical synthesis was performed by potentiostatic synthesis at 1 V. The chemical characterization of the material before and after Pani polymerization was performed by means of X-ray photoelectron spectroscopy (XPS), energy dispersive X-ray (EDX) and Fourier transform infrared spectroscopy (FTIR). The morphology of the coatings was observed employing scanning electron microscopy (SEM). The electrochemical characterization was performed by cyclic voltammetry (CV) and scanning electrochemical microscopy (SECM). It has been demonstrated that scan rate is an important parameter that influences the response obtained when characterizing conducting fabrics by CV. High scan rates do not allow the observation of redox peaks. However if lower scan rates are employed its apparition has been reported. The electrochemical deposit of polyaniline enhances the electroactivity of the material as it has been demonstrated by CV. SECM measurements showed local response with positive feedback (electroactive material) for the samples in open circuit conditions. XPS analysis also showed a higher doping level (N +/N), consistent with higher material electroactivity. © 2011 Elsevier B.V.Authors thank to the Spanish Ministerio de Ciencia y Tecnologia and European Union Funds (FEDER) (contract CTM2007-66570-C02-02 and CTM2010-18842-C02-02) and Universidad Politecnica de Valencia (Primeros Proyectos de Investigacion (PAID-06-10)) for the financial support. j. Molina is grateful to the Conselleria d'Educacio (Generalitat Valenciana) for the FPI fellowship. A.I. del Rio is grateful to the Spanish Ministerio de Ciencia y Tecnologia for the FPI fellowship.Molina Puerto, J.; Fernández Sáez, J.; Del Río García, AI.; Bonastre Cano, JA.; Cases Iborra, FJ. (2011). Electrochemical synthesis of polyaniline on conducting fabrics of polyester covered with polypyrrole/PW12O403-. Chemical and electrochemical characterization. Synthetic Metals. 161(11-12):953-963. doi:10.1016/j.synthmet.2011.02.029S95396316111-1

Microencapsulation of cerium and its application in sol-gel coatings for the corrosion protection of aluminum alloy AA2024

[EN] Cerium-containing microcapsules were obtained by means of water/oil (W/O) emulsion technology using tetraethyl orthosilicate (TEOS) as the precursor. Synthesis parameters as water/ethanol molar ratio, surfactant concentration, temperature, synthesis time, were optimized to obtain microcapsules with adequate form and size. Cerium salt is a corrosion inhibitor. Scanning electron microscopy (SEM) was employed to characterize the microcapsules and EDS and energy dispersive X-ray (EDX) microanalysis to assess encapsulation of cerium. The synthesized microcapsules were incorporated in the sol-gel coating that was sprayed on AA2024 aluminum alloy. The morphology of the sol-gel coating and the distribution of the microcapsules were investigated by SEM and EDX and the corrosion resistance of the coated samples was evaluated by electrochemical impedance spectroscopy (EIS) and open circuit potential measurements. Cerium microcapsules can act as Ce nanoreservoirs blocking defects produced in the organic-inorganic hybrid coating by precipitating Ce oxide/ hydroxide and nanoloads slowing the diffusion of redox species to the aluminum surface. Higher corrosion resistance was obtained with microencapsulation of cerium than with nonencapsulated cerium.Authors wish to thank to the Instituto Valenciano de Competitividad Empresarial (IVACE) (project reference IMAMCC/2016/1) for the financial support. Electron Microscopy Service of the UPV (Universitat Politecnica de Valencia) is gratefully acknowledged for help with FESEM and EDX characterization.Valero-Gómez, A.; Molina Puerto, J.; Pradas, S.; López-Tendero, MJ.; Bosch, F. (2020). Microencapsulation of cerium and its application in sol-gel coatings for the corrosion protection of aluminum alloy AA2024. 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Woodhead Publishing, Sawston, Cambridge. https://www.elsevier.com/books/rare-earth-based-corrosion-inhibitors/forsyth/978-0-85709-347-9Figueira RB, Silva CJR, Pereira EV (2015) Organic–inorganic hybrid sol–gel coatings for metal corrosion protection: a review of recent progress. J Coat Technol Res 12:1–35Danks AE, Hall SR, Schnepp Z (2016) The evolution of ‘sol–gel’ chemistry as a technique for materials synthesis. Mater Horiz 3:91–112Kumar N, Subasri R (2012) Corrosion protection and self-healing by sol-gel process: a review of recent patent literature. Recent Pat Corros Sci 2:148–163Montemor MF (2014) Functional and smart coatings for corrosion protection: a review of recent advances. Surf Coat Technol 258:17–37Palomino LM, Suegama PH, Aoki IV, Montemor MF, De Melo HG (2009) Electrochemical study of modified cerium–silane bi-layer on Al alloy 2024-T3. 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Prog Org Coat 90:425–430Abourayana HM, Dowling DP (2015) Plasma processing for tailoring the surface properties of polymers. In: Aliofkhazraei M (ed), Surface energy. InTech, London. https://www.intechopen.com/books/surface-energyZille A, Oliveira FR, Souto AP (2015) Plasma treatment in textile industry. Plasma Process Polym 12:98–131Williams DF, Kellar EJC, Jesson DA, Watts JF (2017) Surface analysis of 316 stainless steel treated with cold atmospheric plasma. Appl Surf Sci 403:240–247Kim MC, Yang SH, Boo J-H, Han JG (2003) Surface treatment of metals using an atmospheric pressure plasma jet and their surface characteristics. Surf Coat Technol 174–175:839–844Ciriminna R, Sciortino M, Alonzo G, de Schrijver A, Pagliaro M (2011) From molecules to systems: sol-gel microencapsulation in silica-based materials. Chem Rev 111:765–789Ciriminna R, Fidalgo A, Pandarus V, Béland F, Ilharco LM, Pagliaro M (2013) The sol−gel route to advanced silica-based materials and recent applications. 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