High performance maleated lignocellulose epicarp fibers for copper ion removal

Natural lignocellulosic fiber epicarp extracted from the babassu coconut (Orbignya speciosa) was chemically modified through reaction with molten maleic anhydride without solvent, with incorporation of 189.34 mg g-1 of carboxylic acid groups into the biopolymer structure. The success of this reaction was also confirmed by the presence of carboxylic acid bands at 1741 and 1164 cm-1 in the infrared spectrum. Identically, the same group is observed through 13C NMR CP/MAS in the solid state, via high field signals in the 167 pm region. Both the precursor and the immobilized maleated biopolymers presented nearly the same thermal stability and similar crystallinity to cellulose. However, the pendant carboxylic groups have the ability to remove copper with maximum sorption through a batchwise process at pH 6.0, as expected from the point of zero charge, determined to be 6.45. The sorption kinetic data were fitted to pseudo-first order, pseudo-second order, Elovich-chemisorption and intra-particle diffusion models and the equilibrium data were fitted to the Langmuir, the Freundlich and Tenkim isotherm models. Taking into account a statistical error function and determination coefficients, the data were fit to the pseudo-first and pseudo-second order kinetic and Langmuir isotherm models, with a maximum sorption capacity of copper ions of 55.09 mg g-1. This value suggests the application of this biopolymer with incorporated carboxylate groups as a favorable agent for copper removal from appropriate systems31118319

Effects of heat treatment on the catalytic activity and methanol tolerance of carbon-supported platinum alloys

This work studies the effect of heat treatment of carbon-dispersed platinum and platinum alloys on its methanol tolerance and catalytic activity as gas diffusion electrodes for oxygen reduction reaction (ORR) in acid medium. The catalyst powders were subjected to heat treatments at three different temperatures for a fixed period at controlled atmospheres. Differences in catalyst morphology were characterized using X-ray diffraction, energy dispersive X-ray analysis and transmission electron microscope techniques. The electrochemical characteristics and activity of the electro-catalysts were evaluated for ORR and methanol tolerance using cyclic voltammetry, in the form of gas diffusion electrodes. The optimum heat-treatment temperature is found to be strongly dependent on the individual catalyst. The maximum ORR activity and better methanol tolerance for the oxygen reduction reaction (ORR) was observed in Pt-Fe/C and Pt-Cu/C catalysts subjected to heat treatment at 350 °C.A trend of catalytic activity for oxygen reduction reaction (ORR) was obtained: Pt-Cu/C (350°C)>Pt-Fe/C (350°C) > Pt-Ni/C (350°C) > Pt-Co/C (250°C) > Pt/C (350°C), showing that Pt-Cu/C-type catalysts had a higher catalytic activity with reasonable methanol tolerance

Co3O4 Nanocrystals on Graphene as a Synergistic Catalyst for Oxygen Reduction Reaction

Catalysts for oxygen reduction and evolution reactions are at the heart of key renewable energy technologies including fuel cells and water splitting. Despite tremendous efforts, developing oxygen electrode catalysts with high activity at low costs remains a grand challenge. Here, we report a hybrid material of Co3O4 nanocrystals grown on reduced graphene oxide (GO) as a high-performance bi-functional catalyst for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). While Co3O4 or graphene oxide alone has little catalytic activity, their hybrid exhibits an unexpected, surprisingly high ORR activity that is further enhanced by nitrogen-doping of graphene. The Co3O4/N-doped graphene hybrid exhibits similar catalytic activity but superior stability to Pt in alkaline solutions. The same hybrid is also highly active for OER, making it a high performance non-precious metal based bi-catalyst for both ORR and OER. The unusual catalytic activity arises from synergetic chemical coupling effects between Co3O4 and graphene.Comment: published in Nature Material

Unassisted solar lignin valorisation using a compartmented photo-electro-biochemical cell

Lignin is a major component of lignocellulosic biomass. Although it is highly recalcitrant to break down, it is a very abundant natural source of valuable aromatic carbons. Thus, the effective valorisation of lignin is crucial for realising a sustainable biorefinery chain. Here, we report a compartmented photo-electro-biochemical system for unassisted, selective, and stable lignin valorisation, in which a TiO2 photocatalyst, an atomically dispersed Co-based electrocatalyst, and a biocatalyst (lignin peroxidase isozyme H8, horseradish peroxidase) are integrated, such that each system is separated using Nafion and cellulose membranes. This cell design enables lignin valorisation upon irradiation with sunlight without the need for any additional bias or sacrificial agent and allows the protection of the biocatalyst from enzymedamaging elements, such as reactive radicals, gas bubbles, and light. The photo-electrobiochemical system is able to catalyse lignin depolymerisation with a 98.7% selectivity and polymerisation with a 73.3% yield using coniferyl alcohol, a lignin monomer

Probing the active site in single-atom oxygen reduction catalysts via operando X-ray and electrochemical spectroscopy

[[abstract]]Nonnoble metal catalysts are low-cost alternatives to Pt for the oxygen reduction reactions (ORRs), which have been studied for various applications in electrocatalytic systems. Among them, transition metal complexes, characterized by a redox-active single-metal-atom with biomimetic ligands, such as pyrolyzed cobalt–nitrogen–carbon (Co–Nx/C), have attracted considerable attention. Therefore, we reported the ORR mechanism of pyrolyzed Vitamin B12 using operando X-ray absorption spectroscopy coupled with electrochemical impedance spectroscopy, which enables operando monitoring of the oxygen binding site on the metal center. Our results revealed the preferential adsorption of oxygen at the Co2+ center, with end-on coordination forming a Co2+-oxo species. Furthermore, the charge transfer mechanism between the catalyst and reactant enables further Co–O species formation. These experimental findings, corroborated with first-principle calculations, provide insight into metal active-site geometry and structural evolution during ORR, which could be used for developing material design strategies for high-performance electrocatalysts for fuel cell applications.[[notice]]補正完

Copper sorption from aqueous solutions and sugar cane spirits by chemically modified babassu coconut (Orbignya speciosa) mesocarp

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)The present investigation explores the chemical modification of natural dry babassu coconut (Orbignya speciosa) mesocarp (BM), using a quasi solvent-free procedure in which the precursor was added to molten succinic (S), maleic (M) or phthalic (P) anhydrides, to give new products named BMS, BMM and BMP (babassu coconut mesocarp modified with succinic, maleic and phthalic anhydride, respectively). These synthesized biopolymers were characterized by infrared spectroscopy and thermogravimetry and the degree of substitution was calculated, based on the number of carboxylic groups covalently attached to the lignocellulosic polymer. The chemically modified biopolymers suspended in aqueous or hydroalcoholic solutions have the ability to remove copper from aqueous or aqueous-alcohol solutions in the order BMS > BMP > BMM. The kinetic process followed a pseudo-second-order model and the results for sorbents were better represented by the Langmuir sorption model. The effectiveness of these biopolymers for application to real samples of sugar cane spirits reflected in using only 1.0 g dm(-3) to reduce the copper to a value lower than 5.0 mg dm(-3) for all sorbents. Thus, these inexpensive chemically modified biopolymers may be useful to permit sugar cane spirits to meet the requirements of Brazilian legislation with respect to copper contamination. (C) 2010 Elsevier B.V. All rights reserved.1614167199105Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)FAPEMAConselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq

Removal of textile dyes from aqueous solution by babassu coconut epicarp (Orbignya speciosa)

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Babassu coconut (Orbignya speciosa) epicarp (BCE) was used as biomass to remove textile dyes from aqueous solution. Physical characteristics of the BCE were investigated using infrared spectroscopy (IR), point of zero charge (pH(pzc)), surface area, pore volume and diameter. A batch system was applied to study the sorption of Blue Remazol R160 (BR 160), Rubi S2G (R S2G), Red Remazol 5R (RR 5). Violet Remazol 5R (VR 5) and Indanthrene Olive Green (IOG) dye solutions by BCE. The effects of contact time and concentration on the sorption of the textile dyes onto the BCE were investigated. The interactions were assayed with respect to the pseudo-first-order, pseudo-second-order and the Elovich kinetic models by linear and non-linear regression methods, and were found to follow closely the pseudo-second-order. The ability of babassu coconut epicarp to sorb dyes gave the ordered set BR 160>VR 5>RR 5>R S2G >IOG. Equilibrium data also were fitted by linear and non-linear regression methods through the Langmuir, the Freundlich, the Temkin and the Dubinin-Radushkevich isotherm models. The equilibrium data were best represented by the Dubinin-Radushkevich, showing physical interactions between the species. (C) 2011 Elsevier B.V. All rights reserved.1732334340Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)FAPEMAConselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq

Kinetics and thermodynamics of textile dye adsorption from aqueous solutions using babassu coconut mesocarp

Extracted babassu coconut (Orbignya speciosa) mesocarp (BCM) was applied as a biosorbent for aqueous Blue Remazol R160 (BR 160), Rubi S2G (R S2G), Red Remazol 511 (RR 5), Violet Remazol 5R (VR 5) and Indanthrene Olive Green (IOG) dye solutions. The natural sorbent was processed batchwise while varying several system parameters such as stirring time, pH and temperature. The interactions were assayed with respect to both pseudo-first-order and second-order reaction kinetics, with the latter the more suitable kinetic model. The maximum adsorption was obtained at pH 1.0 for all dyes due to available anionic groups attached to the structures, which can be justified by pH(pzc) 6.7 for the biosorbent BCM. The ability of babassu coconut mesocarp to adsorb dyes gave the order R S2G > VR 5 > BR 160 > IOG > RR 5, which data were best fit to Freundlich model, but did not well-adjusted for all dyes. The dye/biopolymer interactions at the solid/liquid interface are all spontaneous as given by free Gibbs energy, with exothermic enthalpic values of -26.1, -15.8, -17.8, -15.8 and -23.7 kJ mol(-1) for BR 160, R S2G, RR 5, IOG and VR 5, respectively. In spite of the negative entropic values contribution, the set of thermodynamic data is favorable for all dyes removal. However, the results pointed to the effectiveness of the mesocarp of babassu coconut as a biosorbent for removing textile dyes from aqueous solutions. (C) 2009 Elsevier B.V. All rights reserved.166417001272127