Effect of phosphorous groups on the stabilization and activation of low-cost lignin fibers prepared by electrospinning

The feasible wider use of carbon fibers in many of their current and potential applications demands a reduction of their manufacturing costs. In this sense, the use of lignin as an abundant, renewable and low-cost carbonaceous precursor and a simple and versatile production technique, such as the electrospinning, represents an advantageous and promising approach [1-3]. Particularly, the devIlopment of high-value co-products from lignocellulosic biomass-derived industries, such as biorefineries and pulp and paper mills, could suppose a significant opportunity to reduce their associated costs and environmental impacts. However, the use of lignin itself in the production of carbon fibers requires of successive stabilization and carbonization steps that currently slow down, raises the price and, therefore, limits their commercialization and industrial application. In this work, a new method to produce novel sub-micrometer carbon fibers by electrospinning of phosphorous-containing lignin solutions is proposed.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

Novel lignin-based fibrous carbon materials

Lignin is (and will be) an important co-product in many lignocellulosic biomass-derived industries, such as pulp and paper mills (and the future biorefineries, when the concept of bio-economy be developed). The development of high-value products from lignin could mean a significant opportunity to reduce the associated costs and the environmental impacts of these industries [1]. In this sense, a new method to produce novel sub-micrometer carbon fibers and interconnected fibrous carbon webs materials (FCMs), showing unique advanced properties for different applications, by electrospinning [2] of phosphorous-containing lignin solutions is studied in this work. The different FCMs were prepared by electrospinning of Alcell lignin solutions with and without P–containing compounds, followed by stabilization and carbonization at different temperatures. For comparison purposes, equivalent lignin-based powdery carbon materials (PCMs) were also prepared from lignin powder without the electrospinning step. The different samples were characterized by N2 and CO2 adsorption, SEM, TEM, XRD, Raman, XPS, TPD and TG analysis. In the absence of P-containing groups, electrospun carbon fibers are continuous and linear (Fig 1.a), and show a specific surface area of 700 m2/g, much higher than that of carbon prepared in powdery shape (70 m2/g). The presence of P precursors in the lignin solution re-markably affects the electrospinning, sta-bilization and carbo-nization processes. By a suitable control of the stabilization heating rate, continuous and curly carbon fibers (Fig 1.b) or interconnected carbon fibrous webs (Fig 1.c) can be produced. In addition, the presence of 30wt% of P-containing compound in the lignin solution increases the specific surface area up to 1500 m2/g and enhances the oxidation resistance of the FCMs at high temperatures, what have been found very interesting for different applications, such as catalysis, adsorption and energy storage and conversion. These properties cannot be obtained in lignin-based carbon powders, even by using an 80wt% of P-containing compound for their chemical activation (1100 m2/g).Universidad de Málaga. Campus de Excelencia Andalucía Tech

Efecto del H3PO4 en la preparación de fibras de carbono a partir de lignina. Mejoras en el proceso de estabilización y propiedades finales

El presente trabajo propone un nuevo método de preparación de fibras de carbono mediante electrohilado de mezclas de lignina/H3PO4, en el que se obtienen resultados que aceleran el proceso de preparación de estos materiales así como sus propiedades físico-químicas en una sola etapa de preparación. Será objeto de estudio la temperatura, tiempo y velocidad de calentamiento en la etapa de estabilización así como la atmósfera (inerte u oxidante) de estabilización y carbonización.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

Electrochemical behavior of pt- a d pd-supported activated carbons with different functionalities

Due to their relatively low price, high surface area and versatile physic-chemical properties, conductive carbon materials are considered among the most promising supports of electroactive species and/or catalysts for different electrochemical devices, like supercapacitors, fuel cells, batteries, sensors, etc. [1]. However, in these applications, carbon supports are usually subjected to oxidation and/or corrosion processes, which can be promoted by the supported electroactive species and/or catalysts [2]. In this sense, although the surface functionalities of carbons seem to play a key role on their electrochemical response and stability, their influence in the presence of electroactive catalysts is still controversial. Particularly, the effect of phosphorous groups has been never reported. In this work, the influence of different oxygen and phosphorous functionalities on the electrochemical behavior of Pt- and Pd-supported activated carbons (ACs) has been studied. Various ACs showing similar surface areas (ca. 1400-1500 m2/g) and a rich variety of surface chemistry, with oxygen and phosphorous-like surface groups, were obtained by physical (CO2) (HAG800 support) or chemical (H3PO4) (HA3500 support) activation of olive stone. The ACs were used as support of Pd, Pt and Pd/Pt catalysts (Fig 1a), with nominal loadings of 0.5-1.0 wt%, by using the incipient-wetting impregnation method. The samples were characterized by N2 and CO2 adsorption, TEM, XRD, XPS, TPD experiments and different electrochemical techniques. Although the supported metals promote carbon electroxidation and/or corrosion (see the higher oxidation currents for the metalloaded sample – Fig 1b), the presence of surface phosphorous groups (HA3500-M samples) results in lower oxidation currents than in the case of P-free samples (HAG800-M samples) (Fig. 1.b). These results are in agreement with the oxidation resistance induced by phosphorous groups in oxidizing gas phase at high temperatures [3], and may support the statement that these phosphorous groups could enhance the durability of carbon-supported metal electrocatalysts for different electrochemical applications.Universidad de Málaga. Campus de Excelencia Andalucía Tech

Comportamiento electroquímico de carbones activados con presencia de grupos superficiales de fósforo

Debido a su elevada superficie específica y una combinación única de conductividad, estabilidad y gran versatilidad química-estructural, los carbones activados (CAs) se emplean como electrodos en diversas aplicaciones electroquímicas. En estas aplicaciones, los heteroátomos presentes en su superficie, tales como oxígeno y nitrógeno, juegan un papel muy importante. La presencia de grupos superficiales estables de fósforo ha sido menos estudiada, pero parece inducir efectos positivos en las propiedades electroquímicas de los materiales carbonosos, aumentando su conductividad, capacidad y/o actividad electrocatalítica en diversas reacciones. Además, se ha propuesto que dichos grupos aumentan la resistencia a la oxidación electroquímica del material en medio acuoso, lo que supone una prometedora aproximación para aumentar la densidad de energía de los supercondensadores en este medio. No obstante, a pesar de todas estas ventajas, no existen estudios que justifiquen las causas ni los mecanismos de tales efectos. En este trabajo se presenta un estudio sobre el efecto de los grupos superficiales de fósforo en la capacidad y la estabilidad electroquímica de un carbón activado.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

Preparación de micro-supercondensadores mediante electrosprayado de materiales carbonosos nanoestructurados

Los materiales carbonosos nanoestructurados presentan excelentes propiedades eléctricas, texturales y estructurales, que pueden ser aprovechadas para la fabricación de microcondensadores de elevada potencia y energía, fundamentales en el desarrollo de dispositivos electrónicos portátiles. Sin embargo, el reducido tamaño de sus partículas dificulta su procesado en láminas delgadas, impidiendo un control adecuado de la forma y el espesor de capas finas de estos materiales. Los procedimientos basados en la preparación directa de materiales carbonosos sobre el colector de corriente condicionan la composición y estructura del electrodo, lo que provoca un aumento de los costes de producción. Por ello, es necesario el desarrollo de nuevos procedimientos de fabricación de capas finas que permitan la completa implementación de estos dispositivos. En este sentido, destaca la técnica de electrosprayado. Esta técnica está basada en las fuerzas electrohidrodinámicas. Cuando un líquido fluye a través de un capilar y se aplica un campo eléctrico (este campo eléctrico se suele establecer entre el capilar y un colector de corriente plano), el correspondiente menisco se deforma en un cono, conocido como cono de Taylor. Cuando el voltaje del campo eléctrico alcanza un determinado valor límite, las fuerzas electrohidrodinámicas superan la tensión superficial del líquido, produciendo la salida de un chorro de pequeño diámetro. Generalmente, ese chorro rompe formando un espray, formado por gotas de tamaño nanométrico altamente cargadas. En este trabajo se propone el uso de la técnica de electrosprayado para el depósito controlado de una lámina delgada y continua de un material carbonoso nanoestructurado, directamente sobre el colector de corriente. Las láminas delgadas resultantes fueron caracterizadas como electrodos en supercondensadores con un electrolito acuoso.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tec

In situ characterization of porous VPO catalysts with fibrous structure: Identifying the redox behavior and the stability of active sites

Two VPO materials with fibrillar morphology have been prepared by the aid of electrospinning technique. One is a VPO carbon-supported material (VCF200) with fibrous morphology and very high surface area that is stable under oxidizing conditions up to 350C. The other material is a bulk mixed VPO oxide (VPO500) with fibrous structure obtained after optimizing the calcination of the carbon support in VCF200. Despite it is a bulk oxide material, this material exhibits a high surface area (> 60 m2/g). The redox behavior of both samples was monitored by in situ Raman spectroscopy under oxidation/reduction cycles. For the dehydrated supported sample (VCF200), the pyrophosphate phase (VO)2P2O7 (Raman ~930 cm-1) is detected, which has been described as the active phase (see Figure (a) below). This phase is quite stable since it does not disappear upon subsequent oxidation/reduction cycles. Under reduction conditions at 125C, in consecutive cycles, additional Raman bands appear at ~1090 cm-1 that are characteristic of the αII-VOPO4 phase. On the other hand, the bulk phases show a reversible behavior under redox cycles (Figure (b)). Under reducing conditions, a Raman band appears at ~980 cm-1 (β-VPO phase), whereas under oxidation conditions some segregation to VOx oxides occurs. Nevertheless, this segregation is reversible and the β-VPO phase forms again under reducing conditions. Thus, these results demonstrate that the active VPO phases of these fibrous catalysts are quite stable, and that their structure is reversible under several redox cycles, which make them suitable as oxidation catalysts.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech