Thermochemical Activation of Wood with NaOH, KOH and H3PO4 for the Synthesis of Nitrogen-Doped Nanoporous Carbon for Oxygen Reduction Reaction.

Carbonization of biomass residues followed by activation has great potential to become a safe process for the production of various carbon materials for various applications. Demand for commercial use of biomass-based carbon materials is growing rapidly in advanced technologies, including in the energy sector, as catalysts, batteries and capacitor electrodes. In this study, carbon materials were synthesized from hardwood using two carbonization methods, followed by activation with H3PO4, KOH and NaOH and doping with nitrogen. Their chemical composition, porous structure, thermal stability and structural order of samples were studied. It was shown that, despite the differences, the synthesized carbon materials are active catalysts for oxygen reduction reactions. Among the investigated carbon materials, NaOH-activated samples exhibited the lowest Tafel slope values, of -90.6 and -88.0 mV dec-1, which are very close to the values of commercial Pt/C at -86.6 mV dec-1.

Effect of Pretreatment on the Nitrogen Doped Activated Carbon Materials Activity towards Oxygen Reduction Reaction.

Nitrogen-doped activated carbons with controlled micro- and mesoporosity were obtained from wood and wastes via chemical processing using pre-treatment (pyrolysis at 500 °C and hydrothermally carbonization at 250 °C) and evaluated as oxygen reduction catalysts for further application in fuel cells. The elemental and chemical composition, structure and porosity, and types of nitrogen bonds of obtained catalyst materials were studied. The catalytic activity was evaluated in an alkaline medium using the rotating disk electrode method. It was shown that an increase in the volume of mesopores in the porous structure of a carbon catalyst promotes the diffusion of reagents and the reactions proceed more efficiently. The competitiveness of the obtained carbon materials compared to Pt/C for the reaction of catalytic oxygen reduction is shown.

"Sweetwoods" Lignin as Promising Raw Material to Obtain Micro-Mesoporous Carbon Materials.

Biorefineries with the significant amounts of lignin as a by-product have a potential to increase business revenues by using this residue to produce high value-added materials. The carbon materials from biomass waste increases the profitability of the production of porous carbon used for sorbents and energy production. The purpose of this research is to study the chemical properties of lignin from "Sweetwoods" biorefinery as well as to characterize lignin carbonizates and activated carbons synthesized from them. This paper describes the effect of carbonization conditions (thermal or hydrothermal) on the properties of activated carbon material. It can be concluded that, depending on the carbonization method, the three-dimensional hierarchical porous structure of activated carbon materials based on "Sweetwoods" lignin, has micro- and mesopores of various sizes and can be used for number of purposes: both for high-quality sorbents, catalysts for electrochemical reduction reactions, providing sufficient space for ion mass transfer in electrodes for energy storage and transfer.

Black Liquor and Wood Char-Derived Nitrogen-Doped Carbon Materials for Supercapacitors.

Herein, we present a synthesis route for high-efficiency nitrogen-doped carbon materials using kraft pulping residue, black liquor, and wood charcoal as carbon sources. The synthesized nitrogen-doped carbon materials, based on black liquor and its mixture with wood charcoal, exhibited high specific surface areas (SSAs) of 2481 and 2690 m2 g-1, respectively, as well as a high volume of mesopores with an average size of 2.9-4.6 nm. The nitrogen content was approximately 3-4 at% in the synthesized nitrogen-doped carbon materials. A specific capacitance of approximately 81-142 F g-1 was achieved in a 1 M Na2SO4 aqueous solution at a current density of 0.2 A g-1. In addition, the specific capacitance retention was 99% after 1000 cycles, indicating good electrochemical stability.

Highly Active Wood-Derived Nitrogen-Doped Carbon Catalyst for the Oxygen Reduction Reaction.

In this recent decade, great interest has risen to develop metal-free and cheap, biomass-derived electrocatalysts for oxygen reduction reaction (ORR). Herein, we report a facile strategy to synthesize an electrochemically active nanocarbon material from the renewable and biological resource, wood biomass. The ORR activity of the catalyst material was investigated in 0.1 M KOH solution by employing the rotating disc electrode method. Scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, and Raman spectroscopy were employed to obtain more information about the catalyst material's morphology and composition. The material exhibits outstanding electrocatalytic activity with low onset potential and high current density, similar to that of a commercial Pt/C catalyst in an alkaline medium. The results clearly ascertain that wooden biomass can be easily transformed into novel carbon nanostructures with superior ORR activity and possibility to be used in fuel cells and metal-air batteries.

The Impact of Lignin Structural Diversity on Performance of Cellulose Nanofiber (CNF)-Starch Composite Films.

Lignin fractions having different molecular weights and varied chemical structures isolated from kraft lignins of both softwood and hardwood via a sequential solvent fractionation technique were incorporated into a tunicate cellulose nanofibers (CNF)-starch mixture to prepare 100% bio-based composite films. The aim was to investigate the impact of lignin structural diversity on film performance. It was confirmed that lignin's distribution in the films was dependent on the polarity of solvents used for fractionation (acetone > methanol > ethanol > ethyl acetate) and influenced the optical properties of the films. The ⁻OH group content and molecular weight of lignin were positively related to film density. In general, the addition of lignin fractions led to decrease in thermal stability and increase in Young's modulus of the composite films. The modulus of the films was found to decrease as the molecular weight of lignin increased, and a higher amount of carboxyl and phenolic ⁻OH groups in the lignin fraction resulted in films with higher stiffness. The thermal analysis showed higher char content formation for lignin-containing films in a nitrogen atmosphere with increased molecular weight. In an oxygen atmosphere, the phenol content, saturated side chains and short chain structures of lignin had impacts on the maximum decomposition temperature of the films, confirming the relationship between the chemical structure of lignin and thermo-oxidative stability of the corresponding film. This study addresses the importance of lignin diversities on composite film performance, which could be helpful for tailoring lignin's applications in bio-based materials based on their specific characteristics.

The effects of woodchip- and straw-derived biochars on the persistence of the herbicide 4-chloro-2-methylphenoxyacetic acid (MCPA) in soils.

Sorption and degradation are the primary processes controlling the efficacy and runoff contamination risk of agrochemicals. This study assessed the influence of two biochars, made from woodchips and straw at a pyrolysis temperature of 725°C and applied to a loamy sand and a sandy soil in the concentration of 5.3 g 100 g(-1) sandy soil and 4.1 g 100 g(-1) loamy sand soil, or 53 t ha(-1) for both soil types, on degradation of the herbicide 4-chloro-2-methylphenoxyacetic acid (MCPA). Soils were spiked with 50 mg MCPA kg(-1) soil. In the sandy soil, significantly more MCPA remained after 100 days if amended with straw-derived biochar in comparison to wood-derived biochar. Both biochars types significantly increased urease activity (p<0.05) after 37 days in the loamy sand soil, but these differences disappeared after 100 days. A root and shoot elongation test demonstrated that the soils containing straw-derived biochar and spiked with MCPA, showed the highest phytotoxicity. Both biochars were found to retard MCPA degradation in loamy sand and sandy soils. This effect could not be explained only by sorption processes due to comparatively low developed micro/mesoporous structure of both biochars shown by BET surface analysis. However, an enhanced MCPA persistence and soil toxicity in sandy soil amended with straw biochar was observed and further studies are needed to reveal the responsible mechanisms.