Desarrollo de nuevas membranas compuestas para la separación de iones metálicos y aplicaciones electroquímicas

Consultable des del TDXLas investigaciones recogidas en esta memoria versan sobre el desarrollo de nuevos materiales y membranas con propiedades mejoradas preparados mediante la técnica de Reactivos Incorporados en Fase Sólida (Solid-Phase Incorporated Reagents, SPHINER.). Esta técnica se basa en la incorporación de reactivos en una fase sólida mediante diferentes procedimientos como un primer paso para la preparación de materiales compuestos. Por este medio, se han preparado Membranas Compuesta Activadas (Activated Composite Membranes, ACM) con ácido di-(2-etilhexil)ditiofosfórico como transportador de iones metálicos. Este tipo de membranas son membranas bicapa formadas por un soporte microporoso de polisulfona y una capa densa y delgada de poliamida en la parte superior. En el interior se atrapa el reactivo incorporado que es capaz de formar complejos estables con los metales de interés. En este sentido, las ACM han demostrado su capacidad para el transporte selectivo y efectivo de varios iones metálicos como cinc, cadmio, bismuto, cobre, estaño e indio. A partir de los datos recogidos en el transcurso de las investigaciones, se ha confeccionado un modelo semicuantitativo para predecir el flujo de los iones en un sistema específico en la función de las constantes de equilibrio de las especies implicadas. Además, se ha realizado una caracterización morfológica exhaustiva para asociar los parámetros estructurales de la membrana con sus propiedades de transporte. Esta caracterización ha revelado que la formación de la capa de poliamida sobre soportes de polisulfona comercial produce unas membranas poco satisfactorias sin las propiedades de transporte requeridas. Además, se han preparado nuevos materiales que incorporan en su interior nanopartículas metálicas (Metal Nanoparticles, MNP) mediante el procedimiento de síntesis intermatricial tanto en polímeros funcionalizados como no funcionalizados. De esta manera se ha logrado sintetizar nanopartículas metálicas macizas y también nanopartículas mixtas con estructura "core-shell". Las nanopartículas formadas han sido caracterizadas por diferentes técnicas microscópicas para saber su tamaño, su distribución y su grado cristalino. Todos los parámetros determinados han sido considerados satisfactorios. Finalmente, los nanoobjetos desarrollados han sido incorporados como membranas sensoras en sensores amperométricos y, como resultado, su eficiencia ha aumentado considerablemente.The research reported in this is memory deals with the development of new membranes and materials with enhanced properties prepared by using the SPHINER technique. This technique consists in the incorporation of reagents in solid phase as a first step to prepare composite materials. By these means, Activated Composite Membranes (ACM) containing di(2-ethylhexyl) dithiophosphoric acid as a carrier have been prepared. This type of membrane are bilayer membranes with a microporous support of polysulfone and a thin dense layer of polyamide in the top. Inside, the incorporated reagent is an extracting agent capable to complex metal ions of interest. The ACM have demonstrated their capacity to selective and effective transport several metal ions such as zinc, cadmium, bismuth, copper, tin and indium. From the data collected in the course of the investigations, a semiquantitative model has been obtained to predict the ion flux for a specific system in function of the equilibrium constant of the involved spices. Moreover, an exhaustive morphological characterization has been carried out in order to link the membrane structure parameters with their transport properties. This characterization has revealed that the formation of the polyamide layer onto commercial polysulfone supports yields to an unsatisfactory composite membranes without transport properties. In addition, new materials containing metal nanoparticles (MNP) have been prepared by inter-matrix synthesis in both functionalized and non-functionalized polymers that behave as synthetic nanoreactors. It has been possible to synthesise bulk metal nanoparticles and core-shell ones. The formed nanoparticles have been characterized by microscopic techniques in order to know their size, distribution, and crystalline degree. All the parameters have been found satisfactory. In addition, the developed nanoobjects have been incorporated in the sensing membranes of amperometric sensors and, as a results, their efficiency has increased considerably

Nanociència : l'important no rau en la noblesa

La nanociència avança dia a dia en el que és el seu camp amb més projecció: les nanopartícules metàl·liques (NPMs). Les excepcionals propietats físico-químiques que les caracteritzen fan possible les seves aplicacions electroquímiques. Aquestes però, poden veure's afectades degut a la tendència de les NPMs a agregar-se, perdent així, la seva forma original. Estabilitzant-les en matrius polimèriques, no només s'ha aconseguit controlar les seves mides i velocitat de creixement, sinó que també poden ser emmagatzemades en forma sòlida i líquida, gràcies a la solubilitat dels polímers. Aquestes aplicacions electroquímiques, tal i com s'explica en el següent article, es basen en l'ús de metalls nobles (partícules monometàl·liques), la qual cosa encareix molt el procés. D'aquí que un dels objectius sigui decréixer la quantitat d'aquests metalls -sense perdre la seva capacitat electrocatalítica- i preparar nanopartícules del tipus nucli-embolcall (bimetàl·liques). Aquestes posseeixen un nucli de metall econòmic recobert per un altre de noble, i han demostrat ser més estables en quant a mida i forma, a més de presentar una activitat electrocatalítica superior.La nanociencia avanza día a día en el que es su campo con más proyección: las nanopartículas metálicas (NPMs). Las excepcionales propiedades físico-químicas que las caracterizan hacen posible sus aplicaciones electroquímicas. Éstas, sin embargo, pueden verse afectadas debido a la tendencia de las NPMs a agregarse, perdiendo, así, su forma original. Estabilizándolas en matrices poliméricas, no sólo se ha conseguido controlar su tamaño y velocidad de crecimiento, sino que también pueden ser almacenadas en forma sólida y líquida, gracias a la solubilidad de los polímeros. Estas aplicaciones electroquímicas, tal como se explica en el siguiente artículo, se basan en el uso de metales nobles (partículas monometálicas), lo que encarece mucho el proceso. De aquí que uno de los objetivos sea disminuir la cantidad de estos metales -sin perder su capacidad electrocatalítica- y preparar nanopartículas del tipo núcleo-envoltorio (bimetálicas). Éstas poseen un núcleo de metal económico recubierto por otro que es noble, y han demostrado ser más estables en cuanto a tamaño y forma, además de presentar una actividad electrocatalítica superior, siempre y cuando se mantenga la misma cantidad de metal noble.The field of metallic nanoparticles (MNP), one of the nanoscience fields with most projection, advances daily. The exceptional characteristic physical and chemical properties of these particles make it possible to use them in electrochemical applications. However, this can be affected by the tendency of MNPs to group together and thus lose their original form. By stabilising the particles in polymeric matrices it is possible not only to control their size and speed of growth, but to store them in solid and liquid forms due to the solubility of polymers. As explained in the following article, noble metals (monometallic particles) are used in electrochemical applications, which make the process extremely expensive. The objective therefore is to reduce the quantity of noble metal used -without compromising electrocatalytic capacity -and add core-shell (bimetallic) nanoparticles. These possess a more economical metal core covered by a noble metal shell. They have been proved to be more stable in both size and shape, and display greater electrocatalytic activity

Preparació de suports biomaterials de naturalesa proteica mitjançant electrofilatura

La electrohilatura se ha postulado como un método sencillo, versátil y escalable a nivel industrial que per-mite obtener nanofibras por aplicación de un campo eléctrico de alto voltaje entre la punta de una aguja, donde se deposita una gota de solución de un polímero, y un colector metálico. Uno de los campos de aplicación más prometedores de esta tecnología es el enfocado al desarrollo de soportes biomateriales para el sector biomédico. Sin embargo, el control de los parámetros del proceso es clave para la obtención de productos eficaces. En este sentido, este trabajo presen-ta un estudio sistemático del efecto de los principales parámetros de la electrohilatura que pueden afectar al diámetro de las fibras obtenidas, enfocado específicamente al desarrollo de soportes biomateriales de naturaleza proteica (gelatina y colágeno), por tratarse de substratos de similar naturaleza a los componentes fibrosos encontrados en las matrices extracelulares de los tejidos biológicos. Los resultados obtenidos indican que factores como el tipo de polímero, la concentración, el disolvente y la conductividad del colector tienen una influencia significativa en el diámetro final de las nanofibras. Sin embargo, no se observó influencia en el diámetro cuando se varió el voltaje, caudal y distancia al colector del sistemaPostprint (published version

Development of novel catalytically active polymer-metal-nanocomposites based on activated foams and textile fibers

In this paper, we report the intermatrix synthesis of Ag nanoparticles in different polymeric matrices such as polyurethane foams and polyacrylonitrile or polyamide fibers. To apply this technique, the polymer must bear functional groups able to bind and retain the nanoparticle ion precursors while ions should diffuse through the matrix. Taking into account the nature of some of the chosen matrices, it was essential to try to activate the support material to obtain an acceptable value of ion exchange capacity. To evaluate the catalytic activity of the developed nanocomposites, a model catalytic reaction was carried out in batch experiments: the reduction of p-nitrophenol by sodium borohydride

Chicken feathers based composites: a life cycle assessment

Chicken feathers (CFs) are a waste material generated from poultry industry in large quantities. A composite material constituted of poly lactide and CFs is proposed in order to prepare a biodegradable composite with low environmental impact. In order to evaluate its environmental impact, a Life Cycle Assessment (LCA) is performed. The results show that, from the environmental point of view, the more chicken feathers in the material, the greater is its impact. This is mainly due to the non - inclusion of the impact data regarding CFs current waste management treatments required in accordance with the European Directive CE 1069/2009 (in study) and to the high energy consumption of the pre - treatment stages (cleaning and sanitizing) required to transform CFs waste into a CFs technical material that can be used for the preparation of CFs/PLA composites material, which needs to be optimized.Peer ReviewedPostprint (published version

Environmental impact assessment of Polylactide(PLA)/chicken feathers biocomposite materials

The aim of this study is to analyse the environmental impacts (EIs) of the process of preparation of new biocomposite materials obtained from polylactide (PLA) and chicken feathers (CFs). Two CFs stabilization methods and different percentages of CFs have been studied. The EIs of these new composites were compared to the impact of virgin PLA. Cradle-to-gate life cycle inventories were assessed for 0–35% v/v of CFs in a CFs/PLA biocomposite. Two CFs stabilization processes, autoclave and surfactant, were tested and compared with the aim to prioritize one of them from the environmental point of view. A composite plate of 184¿×¿184¿×¿2.2 mm3 was defined as the functional unit. Autoclave stabilization process exhibited lower environmental impact compared with surfactant stabilization process mainly due to both the lower requirements of electricity and water and the reduced pollution loads of the generated wastewater. Thus, the autoclave process was selected as the standard method when comparing the EIs of the proposed CFs/PLA biocomposites. In this sense, the addition of CFs to PLA matrix proportionally reduces all the EIs compared to pure PLA due to the replacement of PLA with CFs. This behaviour can be explained because the PLA production accounts for the 99% of the impact of the biocomposite. Consequently, CFs conveniently stabilized might be an alternative raw material to prepare CFs/PLA biocomposites with less environmental impact compared to pure PLAPostprint (author's final draft

Development of novel catalytically active polymer-metal-nanocomposites based on activated foams and textile fibers

In this paper, we report the intermatrix synthesis of Ag nanoparticles in different polymeric matrices such as polyurethane foams and polyacrylonitrile or polyamide fibers. To apply this technique, the polymer must bear functional groups able to bind and retain the nanoparticle ion precursors while ions should diffuse through the matrix. Taking into account the nature of some of the chosen matrices, it was essential to try to activate the support material to obtain an acceptable value of ion exchange capacity. To evaluate the catalytic activity of the developed nanocomposites, a model catalytic reaction was carried out in batch experiments: the reduction of pnitrophenol by sodium borohydridePostprint (published version

Fast fabrication of reusable polyethersulfone microbial biosensors through biocompatible phase separation

In biosensors fabrication, entrapment in polymeric matrices allows efficient immobilization of the biorecognition elements without compromising their structure and activity. When considering living cells, the biocompatibility of both the matrix and the polymerization procedure are additional critical factors. Bio-polymeric gels (e.g. alginate) are biocompatible and polymerize under mild conditions, but they have poor stability. Most synthetic polymers (e.g. PVA), on the other hand, present improved stability at the expense of complex protocols involving chemical/physical treatments that decrease their biological compatibility. In an attempt to explore new solutions to this problem we have developed a procedure for the immobilization of bacterial cells in polyethersulfone (PES) using phase separation. The technology has been tested successfully in the construction of a bacterial biosensor for toxicity assessment. Biosensors were coated with a 300 μm bacteria-containing PES membrane, using non-solvent induced phase separation (membrane thickness≈300 μm). With this method, up to 2.3×106 cells were immobilized in the electrode surface with an entrapment efficiency of 8.2%, without compromising cell integrity or viability. Biosensing was performed electrochemically through ferricyanide respirometry, with metabolically-active entrapped bacteria reducing ferricyanide in the presence of glucose. PES biosensors showed good stability and reusability during dry frozen storage for up to 1 month. The analytical performance of the sensors was assessed carrying out a toxicity assay in which 3,5-dichlorophenol (DCP) was used as a model toxic compound. The biosensor provided a concentration-dependent response to DCP with half-maximal effective concentration (EC50) of 9.2 ppm, well in agreement with reported values. This entrapment methodology is susceptible of mass production and allows easy and repetitive production of robust and sensitive bacterial biosensorsPostprint (author's final draft

Environmental impact of chicken feathers based polypropylene composites developed for automotive and stationary applications and comparison with glass-fibre analogues

In last decades, there has been an interest in using biogenic wastes and by-products as fillers or reinforcements to produce polymer composites. Hence, new composites materials based on a blend of biogenic chicken feathers (CFs) and polypropylene (PP) are proposed in this work and compared, from the environmental point of view, with currently used materials as neat PP and PP reinforced with glass-fibres (PP-GF). A Cradle-to-Grave Life Cycle Assessment (LCA) was performed in order to compare the environmental impact of these three materials when being used either for automotive or stationary applications. The mechanical properties of each material were taken into account to calculate the equivalent mass of each industrial application and the use phase and end of life (EoL) were included in the LCA study. The results showed that, for automotive applications and for all the materials studied (PP-GF, PP-CFs and PP) the use phase has a great contribution to the environmental impact categories considered, proving that the new developed material based on CFs (PP-CFs) would be appropriate for stationary applications but not for mobile applications as automotive ones. In addition, the EoL scenario considered, i.e. incineration with energy recovery, has proven to provide extra environmental creditsOpen Access funding provided thanks to the CRUE-CSIC agreement with Springer Nature. This work was funded by the Spanish Ministerio de Economía y Competitividad. Project ref. MAT2015-65392-C2-1-R (MINECO/FEDER)Postprint (published version

Effect of chemical treatments and additives on properties of chicken feathers thermoplastic biocomposites

The valorization of chicken feathers (CFs) waste was researched in this work through the preparation of composites using ground chicken feathers as a filler (20 % v/v) and polypropylene (PP) or low-density polyethylene (LDPE) matrices. In order to improve the compatibility between CFs and the matrixes two different strategies were followed. First, by the chemical modification of the CFs by either acetylation or silanization and, second, by the addition of adhesion promoters like maleated polypropylene (MAPP) and maleatead polyethylene (MAPE). The effect of those treatments on the physical, mechanical and structural properties of the thermoplastic-CFs biocomposites, which are mainly related to the fibre–matrix compatibility, was analyzed. Results show that the addition of 20 % (vol/vol) of unmodified CFs to the thermoplastic matrices results in a significant decrease of the tensile strength associated to a weak interfacial adhesion was assessed by SEM. However, when the adhesion promoters were added to the mixture, a significant increase in the tensile strength was noticed, particularly when the composites were obtained by a process at 180 °C. On the contrary, acetylation and silane treatments of the CFs did not result in any practical improvement of the macroscopic properties of the biocompositesPostprint (author's final draft