Design, synthesis, characterization and development of novel organic conducting polymers with technological applications

In this thesis, a series of novel organic conducting polymers have been synthesized using alternative methods based on electrochemical techniques, which have allowed to broaden the knowledge in the field of the characterization by means of topological, spectroscopic, electrochemical and structural techniques. Among the variety of synthesis techniques of conducting polymers, layer-by-layer (LbL) has been one of the most important to build multilayered systems. Thus, in this thesis the LbL has shown to be an excellent procedure to explore new applications in the field of energy storage using conducting polymers. On the other hand, recently, the influence of new sustituents on functionalized conducting polymers has been proved to modify the structural, optical and physical properties of conducting polymers. Within this context, synthesis of novel functionalized conducting polymers bearing strong electron-withdrawing sustituents such as cyano group or halide atoms have been widely studied and characterized throughout this thesis. The presence of these substituents have emerged as promising candidates in the field of chemical sensors and electrochromic devices. Although the functionality of polymers or the development of new techniques are excellent procedures to synthesize and to develop new properties on the field of conducting polymers, it is worth mentioning that the substrate plays a crucial role on the electrochemical field. Accordingly, the substrates can also modify and change the properties of conducting polymers during the electropolymerization process. In this way, different substrates were employed in this work with the aim of achieving new applications in the field of corrosion inhibitors and as supercapacitors. Supercapacitors as energy storage device has been an outstanding application during this thesis. Thus, the field of nanotechnology has taken an important part in this thesis through development and design of promising hybrid nanocomposites based on conducting polymers and clay with technological applications and interesting optoelectronic properties. The contribution of theoretical techniques based on quantum mechanical calculations have allowed to predict some electronic and structural properties of conjugated polymers, which could be corroborated experimentally. The quantum mechanics is a useful tool to check experimental results and to understand mechanisms not fully understood at experimental level. Therefore, theoretical calculations have provided promising information to obtain new insights in the field of conducting polymers.La presente tesis se encuentra focalizada en el estudio de nuevos polímeros conductores orgánicos obtenidos a partir de métodos alternativos basados en principios electroquímicos. Entre los principales métodos de polimerización la técnica conocida como capa-a-capa ha emergido con gran fuerza en los últimos años dada sus numerosas ventajas y propiedades. En este contexto, la síntesis de polímeros conductores mediante este procedimiento permitió comprender y analizar el efecto sinérgico entre capas, consiguientemente la caracterización de estos nuevos materiales a partir de técnicas estructurales, espectroscópicas, morfológicas, electroquímicas y ópticas permitió indagar y desarrollar aplicaciones en diferentes campos tecnológicos tales como la electrónica o la corrosión. Otro de los factores que influyen en las propiedades de los polímeros conductores es el proceso de funcionalización. En esta tesis, la incorporación de grupos funcionales con elevado carácter aceptor de electrones centró una parte importante del trabajo, de este modo, los polímeros conductores funcionalizados con átomos halogenados o mediante el grupo ciano evidenciaron una gran influencia en las propiedades físicas, estructurales, ópticas y morfológicas de las estructuras químicas en tiofeno y pirrol. La modificación de determinadas propiedades en estos polímeros permitió desarrollar componentes basados en sensores químicos o dispositivos electrocrómicos. Acorde a esta temática, la modificación de la superficie juega también un papel importante y crucial en las propiedades de los polímeros conductores durante el proceso de síntesis electroquímica. Análogamente al caso de la funcionalización el estudio de la modificación de la superficie denotó una gran expectativa en el desarrollo de nuevos supercondensadores orgánicos, así como una gran alternativa para aplicación como inhibidores de corrosión. Finalmente, en el ámbito experimental de esta tesis, se han orientado estudios en el campo de la nanotecnología en la síntesis y caracterización de nuevos materiales híbridos nanocompuestos con interesantes propiedades optoelectrónicas y electroquímicas. A nivel teórico, la contribución de cálculos teóricos basados en mecánica quántica permitieron predecir determinadas propiedades electrónicas y estructurales de polímeros conductores, cuyos valores fueron corroborados experimentalmente. Así, la química teórica proporcionó un amplio conocimiento en la exploración y comprensión de los mecanismos estructurales de los polímeros conductores

A class of multifunctional smart energy materials

Funding Information: S. Goswami would like to thank to Lisboa2020 Programme, Centro 2020 programme, Portugal 2020, European Union, through the European Social Fund who supported LISBOA-05-3559-FSE-000007 and CENTRO-04-3559-FSE-000094 operations as well as to Fundação para a Ciência e Tecnologia (FCT) and Agência Nacional de Inovação (ANI). Publisher Copyright: © 2022 The AuthorsPolymer material provides significant advantages over the conventional inorganic material-based electronics due to its attractive features including miniaturized dimension and feasible improvisations in physical properties through molecular design and chemical synthesis. In particular, conjugate polymers are of great interest because of their ability to control the energy gap and electronegativity through molecular design that has made possible the synthesis of conducting polymers with a range of ionization potentials and electron affinities. Polyaniline (PANI) is one of the most popular conjugated polymers that has been widely explored so far for its multifunctionality in diverse potential applications. This review is focusing on the recent advances of PANI for smart energy applications including supercapacitors, batteries, solar cells and nanogenerators and the development in its synthesis, design, and fabrication processes. A details investigation on the different types of chemical process has been discussed to fabricate PANI in nanostructures, film, and composites form. The paper includes several studies which are advantageous for understanding: the unique chemical and physical properties of this polymer; and the easily tunable electrical properties along with its redox behavior; and different processes to develop nanostructures, film, or bulk form of PANI that are useful to derive its applicability in smart objects or devices.publishersversionpublishe

Developmet of flexible electrodes and lightweight capacitors

This work has focused on the study and development of hierarchically, flexible electrodes and lightweight capacitor using as a source of flexibility. the y-polyglutamic acid (y-PGA) and as an electroactive polymer the poly(3,4-ethylenedioxythiophene) (PEDOT) in composite with alumina (Al2O3),Initially, the PEDOT/Al2O3 composite electroactive film was studied under different monomers: clay proportion and considering the amphoteric behavior of the Al2O3, the analysis of the pH affectation was done. Further, the multi-step in situ polymerization was studied. The experiments demonstrated that the 4:1 monomer: Al2O3 proportion, the multi-step basic medium (pH 8.8) (due to the proximity to the isoelectric point of the filler) favors the electrochemical properties with respect to pure PEDOT. The aforementioned variables combination displays an increment of 55% in specific capacitance (SC) (141 F g-1) compared to the pristine PEDOT. The values obtained demonstrate the synergetic effect of all the variables mentioned and the participation of the filler as a secondary doping agent facilitating the ion mobility.Secondly, the assembly and development of lightweight electrodes was achieved based on the supramolecular incorporation of PEDOT particles into an aqueous biohydrogel (y-PGA). Subsequently, a 20% w/w PEDOT particles were dispersed to give the electroactive characteristic to the gel, following by an extra step of in situ electropolymerization of poly(hydroxymethyl-3,4- ethylenedioxythiophene) (PHMeDOT) to join and increase the conductive polymer connections. Results revealed that electrochemical performance depends of the polymerization time, in this case, the optimum results obtained was the 7h polimerization electrode with a SC 45.4 ±0.7 mF cm-2 from cyclic voltammetry (CV) and charge-discharge (GCD) long-term stability. Finally, the applicability in lightweight and flexible energy-harvesting systems was verified by the LED bulb test. As a third step, a new solid organic symmetric capacitor was constructed, mingling the best results obtained from the previous studies as discussed. Two self-supported p-doped electrodes of y-PGA, PEDOT microparticles, PHMeDOT (2h electropolymerization) with filler of Al2O3 were produced. The electrodes were joined to a supporting solid ¿-PGA electrolyte doped with NaHCO3 salt from the synthesis step and functioning later as the electrolyte The electrochemical performance suggested an excellent prototype stability after 2000 charge-discharge cycles evidencing through an only 8% SC loss, evidencing an excellent stability.This thesis also focused in the n-doped PEDOT-polycation ionene electrode development. As a first step, a synthetic electrochemical protocol was followed to produce an n-doped PEDOT using macromolecular dopant agent, specifically, 1,4- diazabicyclo[2.2.2]octane-based ionene bearing N,N’-(meta-phenylene)dibenzamide linkages (mPi) was established. The protocol consisted of a three-step process , individually optimized: (1) preparation of p-doped (oxidized) PEDOT at a constant potential of +1.40 V in acetonitrile with LiClO4 as electrolyte; (2) dedoping of oxidized PEDOT using a fixed potential of –1.30 V in water; and (3) redoping of dedoped PEDOT applying a reduction potential of –1.10 V in water with mPI. The results obtained displayed a comparable doping level with respect tothe doping level obtained in case of TMA. Nevertheless, the PEDOT doped with mPi revealed better thermal stability and hydrophilicity than the former pristine p-doped and dedoped PEDOT. The final work, considers the influence of the ionene topology on the properties of n-doped PEDOT by comparing three isomeric topomers. The highest doping level was obtained for the para-isomeric ionene-containing electrode, even though the content of ortho- and meta-topomers into the corresponding ndoped PEDOT:ionene electrodes is greater , the topomers interactions as well were related with the hydrogelation of the ionenes.Este trabajo se ha centrado en el estudio jerárquico y desarrollo de electrodos flexibles y condensadores livianos utilizando como fuente de flexibilidad. el ácido ¿-poliglutámico (¿-PGA) y como polímero electroactivo el poli (3,4-etilendioxitiofeno) (PEDOT) en compuesto con alúmina (Al2O3), Inicialmente, la película electroactiva compuesta PEDOT / Al2O3 se estudi ó bajo diferentes proporciones de monómeros:Al2O3 y considerando el comportamiento anfótero del Al2O3, se realizó el análisis de la afectación del pH. Los experimentos demostraron que la proporción 4: 1, multicapa en medio básico (pH 8,8) (debido a la proximidad al punto isoeléctrico de la carga) favorece las propiedades electroquímicas con respecto al PEDOT puro. La combinación de las variables antes mencionadas resultan en un incremento de 55% de la capacitancia espec ífica (SC) (141 F g-1) en comparación con el PEDOT, por sí mismo. Los valores obtenidos demuestran el efecto sinérgico de todas las variables mencionadas y la participación del filler como agente dopante secundario facilitando la movilidad i ónica. En segundo lugar, el ensamblaje y desarrollo de electrodos ligeros se logr ó en base a la incorporación supramolecular de partículas de PEDOT en un bio-hidrogel acuoso (¿-PGA). Posteriormente, se dispersaron partículas de PEDOT al 20% m / m confiriendo la característica electroactiva al gel, seguido de una etapa adicional de electropolimerizaci ón in situ de poli (hidroximetil-3,4-etilendioxitiofeno) (PHMeDOT) para establecer conexiones entre las partículas de PEDOT e incrementar la conductividad. Los resultados indicaron que el rendimiento electroquímico depende del tiempo de polimerizaci ón, en este caso, los resultados óptimos obtenidos fue para el electrodo polimerizado 7h con un SC 45.4 ± 0.7 mF cm-2 de voltametría cíclica (CV) y mostrando una alta electro estabilidad. Finalmente, la aplicabilidad en sistemas ligeros y flexibles de almacenamiento de energía fue verificada con la prueba de la bombilla LED. Como tercer paso, se construyó un nuevo condensador simétrico orgánico sólido, basados en el know-how desarrollado de los estudios previos. Se produjeron dos electrodos p-dopados auto-soportados de ¿-PGA, micropartículas PEDOT, PHMeDOT (electropolimerización 2h) con relleno de Al2O3. Los electrodos se unieron a un electrolito de ¿-PGA sólido dopado con sal de NaHCO3 desde la etapa de s íntesis. El rendimiento electroquímico sugirió una excelente estabilidad del prototipo después de 2000 ciclos de carga y descarga, con s ólo una pérdida de SC del 8%. Esta tesis también se centró en el desarrollo del electrodo de ioneno - polietileno PEDOT n-dopado. Como primer paso, se siguió un protocolo de síntesis electroquímica para producir un PEDOT n-dopado utilizando un agente dopante macromolecular, específicamente, ioneno basado en 1,4-diazabiciclo [2.2.2] octano con N, N '- (meta-fenileno) dibenzamida (mPi). El protocolo consistió en un proceso de tres pasos, optimizados individualmente: (1) preparaci ón de PEDOT pdopado (oxidado) a un potencial constante de +1.40 V en acetonitrilo con LiClO4 como electrolito;(2) desdopadp de PEDOT oxidado utilizando un potencial fijo de -1,30 V en agua; y (3) redopado del PEDOT desdopado aplicando un potencial de reducción de -1.10 V en agua con mPI. Los resultados obtenidos muestran un nivel de dopaje comparable con respecto al nivel de dopaje obtenido en el caso de TMA. Sin embargo, el PEDOT dopado con mPi revel ó una mejor estabilidad térmica e hidrofilicidad que el antiguo PEDOT p-dopado y el desdopado . El trabajo final, considera la influencia de la topolog ía ioneno en las propiedades de PEDOT n-dopado mediante la comparaci ón de tres topómeros isoméricos.El nivel más alto de dopaje se obtuvo para el electrodo que contiene ioneno para-isomérico, aunque el contenido de orto y meta en los correspondientes electrodos de PEDOT: ioneno es mayor, las interacciones topoméricas también se relacionaron con la formación de gelPostprint (published version

Developmet of flexible electrodes and lightweight capacitors

This work has focused on the study and development of hierarchically, flexible electrodes and lightweight capacitor using as a source of flexibility. the y-polyglutamic acid (y-PGA) and as an electroactive polymer the poly(3,4-ethylenedioxythiophene) (PEDOT) in composite with alumina (Al2O3),Initially, the PEDOT/Al2O3 composite electroactive film was studied under different monomers: clay proportion and considering the amphoteric behavior of the Al2O3, the analysis of the pH affectation was done. Further, the multi-step in situ polymerization was studied. The experiments demonstrated that the 4:1 monomer: Al2O3 proportion, the multi-step basic medium (pH 8.8) (due to the proximity to the isoelectric point of the filler) favors the electrochemical properties with respect to pure PEDOT. The aforementioned variables combination displays an increment of 55% in specific capacitance (SC) (141 F g-1) compared to the pristine PEDOT. The values obtained demonstrate the synergetic effect of all the variables mentioned and the participation of the filler as a secondary doping agent facilitating the ion mobility.Secondly, the assembly and development of lightweight electrodes was achieved based on the supramolecular incorporation of PEDOT particles into an aqueous biohydrogel (y-PGA). Subsequently, a 20% w/w PEDOT particles were dispersed to give the electroactive characteristic to the gel, following by an extra step of in situ electropolymerization of poly(hydroxymethyl-3,4- ethylenedioxythiophene) (PHMeDOT) to join and increase the conductive polymer connections. Results revealed that electrochemical performance depends of the polymerization time, in this case, the optimum results obtained was the 7h polimerization electrode with a SC 45.4 ±0.7 mF cm-2 from cyclic voltammetry (CV) and charge-discharge (GCD) long-term stability. Finally, the applicability in lightweight and flexible energy-harvesting systems was verified by the LED bulb test. As a third step, a new solid organic symmetric capacitor was constructed, mingling the best results obtained from the previous studies as discussed. Two self-supported p-doped electrodes of y-PGA, PEDOT microparticles, PHMeDOT (2h electropolymerization) with filler of Al2O3 were produced. The electrodes were joined to a supporting solid ¿-PGA electrolyte doped with NaHCO3 salt from the synthesis step and functioning later as the electrolyte The electrochemical performance suggested an excellent prototype stability after 2000 charge-discharge cycles evidencing through an only 8% SC loss, evidencing an excellent stability.This thesis also focused in the n-doped PEDOT-polycation ionene electrode development. As a first step, a synthetic electrochemical protocol was followed to produce an n-doped PEDOT using macromolecular dopant agent, specifically, 1,4- diazabicyclo[2.2.2]octane-based ionene bearing N,N’-(meta-phenylene)dibenzamide linkages (mPi) was established. The protocol consisted of a three-step process , individually optimized: (1) preparation of p-doped (oxidized) PEDOT at a constant potential of +1.40 V in acetonitrile with LiClO4 as electrolyte; (2) dedoping of oxidized PEDOT using a fixed potential of –1.30 V in water; and (3) redoping of dedoped PEDOT applying a reduction potential of –1.10 V in water with mPI. The results obtained displayed a comparable doping level with respect tothe doping level obtained in case of TMA. Nevertheless, the PEDOT doped with mPi revealed better thermal stability and hydrophilicity than the former pristine p-doped and dedoped PEDOT. The final work, considers the influence of the ionene topology on the properties of n-doped PEDOT by comparing three isomeric topomers. The highest doping level was obtained for the para-isomeric ionene-containing electrode, even though the content of ortho- and meta-topomers into the corresponding ndoped PEDOT:ionene electrodes is greater , the topomers interactions as well were related with the hydrogelation of the ionenes.Este trabajo se ha centrado en el estudio jerárquico y desarrollo de electrodos flexibles y condensadores livianos utilizando como fuente de flexibilidad. el ácido ¿-poliglutámico (¿-PGA) y como polímero electroactivo el poli (3,4-etilendioxitiofeno) (PEDOT) en compuesto con alúmina (Al2O3), Inicialmente, la película electroactiva compuesta PEDOT / Al2O3 se estudi ó bajo diferentes proporciones de monómeros:Al2O3 y considerando el comportamiento anfótero del Al2O3, se realizó el análisis de la afectación del pH. Los experimentos demostraron que la proporción 4: 1, multicapa en medio básico (pH 8,8) (debido a la proximidad al punto isoeléctrico de la carga) favorece las propiedades electroquímicas con respecto al PEDOT puro. La combinación de las variables antes mencionadas resultan en un incremento de 55% de la capacitancia espec ífica (SC) (141 F g-1) en comparación con el PEDOT, por sí mismo. Los valores obtenidos demuestran el efecto sinérgico de todas las variables mencionadas y la participación del filler como agente dopante secundario facilitando la movilidad i ónica. En segundo lugar, el ensamblaje y desarrollo de electrodos ligeros se logr ó en base a la incorporación supramolecular de partículas de PEDOT en un bio-hidrogel acuoso (¿-PGA). Posteriormente, se dispersaron partículas de PEDOT al 20% m / m confiriendo la característica electroactiva al gel, seguido de una etapa adicional de electropolimerizaci ón in situ de poli (hidroximetil-3,4-etilendioxitiofeno) (PHMeDOT) para establecer conexiones entre las partículas de PEDOT e incrementar la conductividad. Los resultados indicaron que el rendimiento electroquímico depende del tiempo de polimerizaci ón, en este caso, los resultados óptimos obtenidos fue para el electrodo polimerizado 7h con un SC 45.4 ± 0.7 mF cm-2 de voltametría cíclica (CV) y mostrando una alta electro estabilidad. Finalmente, la aplicabilidad en sistemas ligeros y flexibles de almacenamiento de energía fue verificada con la prueba de la bombilla LED. Como tercer paso, se construyó un nuevo condensador simétrico orgánico sólido, basados en el know-how desarrollado de los estudios previos. Se produjeron dos electrodos p-dopados auto-soportados de ¿-PGA, micropartículas PEDOT, PHMeDOT (electropolimerización 2h) con relleno de Al2O3. Los electrodos se unieron a un electrolito de ¿-PGA sólido dopado con sal de NaHCO3 desde la etapa de s íntesis. El rendimiento electroquímico sugirió una excelente estabilidad del prototipo después de 2000 ciclos de carga y descarga, con s ólo una pérdida de SC del 8%. Esta tesis también se centró en el desarrollo del electrodo de ioneno - polietileno PEDOT n-dopado. Como primer paso, se siguió un protocolo de síntesis electroquímica para producir un PEDOT n-dopado utilizando un agente dopante macromolecular, específicamente, ioneno basado en 1,4-diazabiciclo [2.2.2] octano con N, N '- (meta-fenileno) dibenzamida (mPi). El protocolo consistió en un proceso de tres pasos, optimizados individualmente: (1) preparaci ón de PEDOT pdopado (oxidado) a un potencial constante de +1.40 V en acetonitrilo con LiClO4 como electrolito;(2) desdopadp de PEDOT oxidado utilizando un potencial fijo de -1,30 V en agua; y (3) redopado del PEDOT desdopado aplicando un potencial de reducción de -1.10 V en agua con mPI. Los resultados obtenidos muestran un nivel de dopaje comparable con respecto al nivel de dopaje obtenido en el caso de TMA. Sin embargo, el PEDOT dopado con mPi revel ó una mejor estabilidad térmica e hidrofilicidad que el antiguo PEDOT p-dopado y el desdopado . El trabajo final, considera la influencia de la topolog ía ioneno en las propiedades de PEDOT n-dopado mediante la comparaci ón de tres topómeros isoméricos.El nivel más alto de dopaje se obtuvo para el electrodo que contiene ioneno para-isomérico, aunque el contenido de orto y meta en los correspondientes electrodos de PEDOT: ioneno es mayor, las interacciones topoméricas también se relacionaron con la formación de ge

State-of-the-art materials science in Belgium 2017

This book is a collection of both review and original research papers which appeared in a Special Issue of the open access journal, Materials, “State-of-the-Art Materials Science in Belgium 2017”. It covers a wide range of selected material topics, currently under investigation at universities throughout Belgium. As a country, Belgium has hardly any physical resources which can be exploited in materials research and development or industry. However, the resource drawback is compensated by focussing on highly technological fields of research, not requiring vast amounts of raw material. This ‘high-tech’ approach includes the development of new analytical methods for the characterization of materials, research into new advanced functional materials, as well as defining new industrial processes for existing materials. As such, the book presents a contemporary view on materials research activities in Belgium

Planet Earth 2011

The failure of the UN climate change summit in Copenhagen in December 2009 to effectively reach a global agreement on emission reduction targets, led many within the developing world to view this as a reversal of the Kyoto Protocol and an attempt by the developed nations to shirk out of their responsibility for climate change. The issue of global warming has been at the top of the political agenda for a number of years and has become even more pressing with the rapid industrialization taking place in China and India. This book looks at the effects of climate change throughout different regions of the world and discusses to what extent cleantech and environmental initiatives such as the destruction of fluorinated greenhouse gases, biofuels, and the role of plant breeding and biotechnology. The book concludes with an insight into the socio-religious impact that global warming has, citing Christianity and Islam

Towards a circular economy: fabrication and characterization of biodegradable plates from sugarcane waste

Bagasse pulp is a promising material to produce biodegradable plates. Bagasse is the fibrous residue that remains after sugarcane stalks are crushed to extract their juice. It is a renewable resource and is widely available in many countries, making it an attractive alternative to traditional plastic plates. Recent research has shown that biodegradable plates made from Bagasse pulp have several advantages over traditional plastic plates. For example, they are more environmentally friendly because they are made from renewable resources and can be composted after use. Additionally, they are safer for human health because they do not contain harmful chemicals that can leach into food. The production process for Bagasse pulp plates is also relatively simple and cost-effective. Bagasse is first collected and then processed to remove impurities and extract the pulp. The pulp is then molded into the desired shape and dried to form a sturdy plate. Overall, biodegradable plates made from Bagasse pulp are a promising alternative to traditional plastic plates. They are environmentally friendly, safe for human health, and cost-effective to produce. As such, they have the potential to play an important role in reducing plastic waste and promoting sustainable practices. Over the years, the world was not paying strict attention to the impact of rapid growth in plastic use. As a result, uncontrollable volumes of plastic garbage have been released into the environment. Half of all plastic garbage generated worldwide is made up of packaging materials. The purpose of this article is to offer an alternative by creating bioplastic goods that can be produced in various shapes and sizes across various sectors, including food packaging, single-use tableware, and crafts. Products made from bagasse help address the issue of plastic pollution. To find the optimum option for creating bagasse-based biodegradable dinnerware in Egypt and throughout the world, researchers tested various scenarios. The findings show that bagasse pulp may replace plastics in biodegradable packaging. As a result of this value-added utilization of natural fibers, less waste and less of it ends up in landfills. The practical significance of this study is to help advance low-carbon economic solutions and to produce secure bioplastic materials that can replace Styrofoam in tableware and food packaging production