Removal of paracetamol on biomass-derived activated carbon: Modeling the fixed bed breakthrough curves using batch adsorption experiments

The remediation of paracetamol (PA), an emerging contaminant frequently found in wastewater treatment plants, has been studied in the low concentration range (0.3–10 mg L−1) using as adsorbent a biomass-derived activated carbon. PA uptake of up to 100 mg g−1 over the activated carbon has been obtained, with the adsorption isotherms being fairly explained by the Langmuir model. The application of Reichemberg and the Vermeulen equations to the batch kinetics experiments allowed estimating homogeneous and heterogeneous diffusion coefficients, reflecting the dependence of diffusion with the surface coverage of PA. A series of rapid small-scale column tests were carried out to determine the breakthrough curves under different operational conditions (temperature, PA concentration, flow rate, bed length). The suitability of the proposed adsorbent for the remediation of PA in fixed-bed adsorption was proven by the high PA adsorption capacity along with the fast adsorption and the reduced height of the mass transfer zone of the columns. We have demonstrated that, thanks to the use of the heterogeneous diffusion coefficient, the proposed mathematical approach for the numerical solution to the mass balance of the column provides a reliable description of the breakthrough profiles and the design parameters, being much more accurate than models based in the classical linear driving force.We gratefully thank Junta de Andalucía (P09-FQM-5156) and Spanish Ministry of Economy and Competitiveness (MINECO – Spain) (Project CTQ2012-36408) and Fondo Europeo de Desarrollo Regional (FEDER – Spain) for financial support

Biomass-derived binderless fibrous carbon electrodes for ultrafast energy storage

The possibility of storing energy efficiently and sustainably at little cost is crucial to prevent climate change and the exhaustion of natural resources. In this work we demonstrate that interconnected and porous carbon fibers easily obtained from lignin exhibit ultrafast charge–discharge and excellent energy density and cyclability performances, to be used as binderless and flexible electrodes in supercapacitors.Financial support by the Spanish Ministerio de Economía y Competitividad, for the MAT2013-42007-P, P09-FQM-5156R, CTQ2012-36408, JCI2011-10566, JCI-2012-12664 and the joint Spanish-Japanese (PRI-PIBJP-2011-0766) projects, FEDER and the Junta de Andalucía is gratefully acknowledged

Activation of electrospun lignin-based carbon fibers and their performance as self-standing supercapacitor electrodes

The production and activation of self-standing carbon electrodes from electrospun lignin fibers was analyzed in this work. Carbon microfibers were prepared at 900 °C from air-stabilized spun cloths by direct carbonization under inert atmosphere and with diluted O2. The modifications of the porosity and surface chemistry of the carbon fibers was also studied by adding H3PO4 in the lignin solution and using different oxygen partial pressures during activation. The presence of phosphoric acid not only increases the porosity development and the preparation yield, but also enhances the gravimetric capacitance of the electrodes. In addition, the activation in presence of oxygen increases the surface area and the generation of wider micropores. Microporous carbon fibers with surface areas as high as 2340 m2 g−1 were obtained using this method. The direct conformation of carbon fibers into binderless electrodes allows to achieve high-power rate capability supercapacitors. Activation in presence of oxygen can enhance up to 50% the energy storage of supercapacitors without compromising the power of the device (8.4 Wh kg−1 and Pmax of 47 kW kg−1). However, at high activation degrees, no further gain in energy density is observed due to the excessive widening of micropores, and the loss of electrical conductivity that increases the cell resistance, limiting the power capability of the device. The optimal results in terms of energy, power and durability are achieved combining low amounts of H3PO4 and mild activation with O2, confirming that electrospinning of lignin is a promising method for sustainable production of self-standing supercapacitor electrodes.We thank MICINN (RTI2018-097555-B-100 and RTI2018-095291-B-I00) for the financial support. F.J.G.M. gratefully acknowledges the assistance of MINECO through a research grant (PTA2015-11464-I)

Sustainable Synthesis of Metal-Doped Lignin-Derived Electrospun Carbon Fibers for the Development of ORR Electrocatalysts

The aim of this work is to establish the Oxygen Reduction Reaction (ORR) activity of self-standing electrospun carbon fiber catalysts obtained from different metallic salt/lignin solutions. Through a single-step electrospinning technique, freestanding carbon fiber (CF) electrodes embedded with various metal nanoparticles (Co, Fe, Pt, and Pd), with 8–16 wt% loadings, were prepared using organosolv lignin as the initial material. These fibers were formed from a solution of lignin and ethanol, into which the metallic salt precursors were introduced, without additives or the use of toxic reagents. The resulting non-woven cloths were thermostabilized in air and then carbonized at 900 °C. The presence of metals led to varying degrees of porosity development during carbonization, improving the accessibility of the electrolyte to active sites. The obtained Pt and Pd metal-loaded carbon fibers showed high nanoparticle dispersion. The performance of the electrocatalyst for the oxygen reduction reaction was assessed in alkaline and acidic electrolytes and compared to establish which metals were the most suitable for producing carbon fibers with the highest electrocatalytic activity. In accordance with their superior dispersion and balanced pore size distribution, the carbon fibers loaded with 8 wt% palladium showed the best ORR activity, with onset potentials of 0.97 and 0.95 V in alkaline and acid media, respectively. In addition, this electrocatalyst exhibits good stability and selectivity for the four-electron energy pathway while using lower metal loadings compared to commercial catalysts.The authors would like to thank the PID2019-105923RB-I00 project funded by MCIN/AEI/10.13039/501100011033, the RTI2018-097555-B-I00 project funded by MICINN and EFRD, and the Generalitat Valenciana (GRISOLIA/2020/114) for the financial support

Controlling the Composition, Morphology, Porosity, and Surface Chemistry of Lignin-Based Electrospun Carbon Materials

Electrospinning is a suitable top-down technique for the preparation of polymeric fibers using high voltage electrical fields and solutions of the selected polymer of adequate viscosity and conductivity. The versatility of electrospinning allows accurate control of the morphology and composition of the fibers by a wide combination of operating conditions and small modifications of the spinneret and collector. Alcell lignin, which is extracted from lignocellulosic biomass using organic solvents through Organosolv process, is readily solved in ethanol, producing a solution that matches the requirements of the electrospinning process. This review summarizes the vast collection of carbon materials that can be obtained by processing lignin using electrohydrodynamic forces. The coaxial and triaxial electrospinning setups allow for obtaining fibers with two or more components hierchically arranged, the use of these configurations along with a carefully setting of the operating conditions (distance between needle and collector, voltage, flow rate,…) and the solution properties (conductivity, viscosity,…) facilitates the conformation of lignin into spheres, beaded fibers, straight fibers and fused meshes. All these morphologies can be implemented with solid or hollow bodies (i.e., enabling the production of tubes and hollow spheres) by using a sacrificial templating agent. Phosphoric acid can also be added in small amounts to the lignin solution, shortening the thermostabilization time of the fibers. The porosity of the phosphorus containing carbon fibers can be modified in the last stage of the preparation of carbon fibers by controlled gasification process, owing to the extended oxidation resistance of the P-doped fibers. Fibrillar carbon catalysts can be also obtained by one-pot preparation method, only solving small quantities of metallic salts in the lignin solution. All these carbon materials were successfully tested in different applications such as heterogeneous catalysis, energy storage and environmental protection, confirming that electrospinning is a powerful tool for maximizing the value of lignin as carbon precursor

Lignin-derived Pt supported carbon (submicron)fiber electrocatalysts for alcohol electro-oxidation

Lignin fibers, with and without phosphorus, and loaded with platinum have been prepared in a single step by electrospinning of lignin/ethanol/phosphoric acid/platinum acetylacetonate precursor solutions. Thermochemical treatments have been carried out to obtain lignin-based carbon fiber electrocatalysts. The electrospun lignin fibers were thermostabilized in air and carbonized at 900 °C. The effect of phosphorus and platinum content on the porous texture, the surface chemistry and the oxidation/electro-oxidation resistance have been studied. Phosphorus-containing carbon fibers develop a higher surface area (c.a. 1200 m2 g−1), exhibit a lower Pt particle size (2.1 nm) and a better particle distribution than their counterpart without phosphorus (c.a. 750 m2 g−1 of surface area and 9.6 nm Pt particle size). It has been proved that phosphorus improves the oxidation and electro-oxidation resistance of the fibers, avoiding their oxidation during the preparation thermal stages and is responsible of the generation of a microporous material with an unusual wide operational potential window (1.9 V). An important Pt–P synergy has been observed in the oxygen transfer during the oxidation and electro-oxidation of the fibers. The obtained carbon fibers can act directly as electrodes without any binder or conductivity promoter. The fibers with platinum have shown outstanding catalyst performance in the electro-oxidation of methanol and ethanol.This work was supported by the Spanish MINECO under CTQ2015-68654-R project

Producción de aromáticos por despolimerización reductiva de lignina sobre catalizadores carbonosos producidos a partir de lignosulfonato sódico.

El incremento de la producción de lignina en la industria de la producción de pasta de celulosa y en las biorefinerías lignocelulósicas, junto con la creciente demanda de procesos con cero producción de residuos en el marco de la bioeconomía circular, hace necesario desarrollar nuevas metodologías para la valorización de la lignina. Este trabajo propone su doble valorización mediante su conversión en catalizadores basados en carbono y la aplicación de éstos en su despolimerización reductiva para la producción de monómeros aromáticos de alto valor añadido. Los carbones activados empleados como soporte catalítico fueron preparados por activación química de un lignosulfonato de sodio con H3PO4 en relación 3/1 (masa agente activante/precursor carbonoso) y activados a 500 °C. El carbón activado fue impregnado con distintas cantidades de sales precursoras de níquel, molibdeno y cobalto y sometido a tratamiento térmico a 800 °C, produciendo un catalizador de níquel y dos catalizadores bimetálicos de Ni-Mo, y Co-Mo. La despolimerización reductiva de lignina organosolv se llevó a cabo empleando estos catalizadores en un reactor discontinuo agitado a 350 °C y 100 bar de presión inicial de H2 durante 4 horas. En todas las reacciones se obtuvo una fase gaseosa, una líquida orgánica, una líquida acuosa y una sólida, las cuales fueron caracterizadas a través de diferentes técnicas. El catalizador carbonoso con Ni y Mo fue el más activo, despolimerizando en gran medida la lignina, y mostrando una moderada actividad en la hidrodesoxigenación de los correspondientes monoméros aromáticos en condiciones suaves. La fase líquida orgánica obtenida presentó un alto rendimiento hacia los monoméros y elevada selectividad hacia aromáticos oxigenados de alto valor económico, como los alquilfenoles. Además, en las pruebas de reacción utilizando como materia prima otra lignina de alto contenido de azufre, el catalizador mantuvo su actividad.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

Fischer-Tropsch synthesis over lignin-derived cobalt-containing porous carbon fiber catalysts

Cobalt-containing lignin-based fibers were synthesized in one step by electrospinning of Alcell lignin solutions as carbon precursor, a low-cost and renewable co-product of the paper making industry. The lignin fibers were thermostabilized in air to avoid the fusion during the carbonization process between 500 and 800 °C to obtain cobalt-containing porous carbon submicron fibers. These carbon fibers catalysts were studied for the Low-Temperature Fischer-Tropsch synthesis. The lignin-derived fibers containing Co catalyst located on the overall carbon fiber surface (internal and external) heat-treated at 500 °C (Co@CF-500) showed the best catalytic performance after 70 h on stream, with 75% and 60% selectivity to C5+ at 220 °C and H2/CO ratios of 1 and 2, respectively, attributed to the high Co dispersion, optimal Co-particle size and better Co accessibility. Higher heat-treatment temperatures leaded to Co-containing carbon fibers with larger metallic cobalt nanoparticles encapsulated in graphitic-type carbon, which rendered them inaccessible for FTS.</p

Methoxylation of a-pinene over mesoporous carbons and microporous

A biomass derived carbon, a commercial microporous carbon and a xerogel mesoporous carbon catalysts were used in the study of a-pinene methoxilation reaction and the influence of textural and physical–chemical properties of the carbons was evaluated. Biomass carbon presented the higher activity, whereas the commercial one is the less active in the conditions studied. The main product of the reaction was a-terpinyl methyl ether and good values of selectivity were obtained over all the catalysts. A kinetic model was developed assuming that the a-pinene is consumed according to the parallel reaction network. The kinetic model presents high quality fittings to the experimental concentration profiles. These results show that it is possible to activate a waste residue using H3PO4 and convert it to high added value product such as acid catalyst