Juan Manuel Sieben

Hydrothermal carbons from hemicellulose-derived aqueous hydrolysis products as electrode materials for supercapacitors.

Acid pretreatment of lignocellulosic biomass, required for bioethanol production, generates large amounts of by-products, such as lignin and hydrolyzed hemicellulose fractions, which have found so far very limited applications. In this work, we demonstrate how the recovered hemicellulose hydrolysis products can be effectively utilized as a precursor for the synthesis of functional carbon materials through hydrothermal carbonization (HTC). The morphology and chemical structure of the synthesized HTC carbons are thoroughly characterized to highlight their similarities with glucose-derived HTC carbons. Furthermore, two routes for introducing porosity within the HTC carbon structure are presented: i) silica nanoparticle hard-templating, which is shown to be a viable method for the synthesis of carbonaceous hollow spheres; and ii) KOH chemical activation. The synthesized activated carbons (ACs) show an extremely high porosity (pore volume≈1.0 cm(3) g(-1)) mostly composed of micropores (90 % of total pore volume). Because of their favorable textural properties, the ACs are further tested as electrodes for supercapacitors, yielding very promising results (300 F g(-1) at 250 mA g(-1)) and confirming the high suitability of KOH-activated HTC carbons derived from spruce and corncob hydrolysis products as materials for electric double layer supercapacitors.

Electro‐Oxidation of Methanol on PtRu Nanostructured Catalysts Electrodeposited onto Electroactivated Carbon Fiber Materials

The surface of different carbon substrates, such as glassy carbon (GC), graphite cloth (GC‐10), graphite felt (GF‐S2), and carbon fiber paper (CFP) was modified by electrochemical treatment to generate high concentrations of oxygenated functional groups. These activated carbons were used as substrates for the simultaneous electrodeposition of Pt and Ru by a double potentiostatic pulse program. The different catalyst/carbon systems were evaluated as electrodes for methanol oxidation in acid solution. Comparing the results for the oxidized and nonoxidized substrates, the oxidation of the different carbon materials prior to the catalyst deposition was found to lead to an increase in the electrode activity for methanol oxidation. This enhancement could be associated with a remarkable improvement of metal dispersion, reduction of particle size, and a higher active surface area of the catalyst. The electrodes prepared with oxidized graphite felt exhibited the greatest catalytic activity.

Pt- and Ru-Doped SnO2–Sb Anodes with High Stability in Alkaline Medium

Different Pt- and Ru-doped Ti/SnO2-Sb electrodes were synthesized by thermal decomposition. The effect of the gradual substitution of Sb by Ru in the nominal composition on the physicochemical and electrochemical properties were evaluated. The electrochemical stability of the electrodes was estimated from accelerated tests at 0.5 A cm(-2) in 1 M NaOH. Both as-synthesized and deactivated electrodes were thoroughly characterized by scanning electron microscopy (SEM), energy-dispersive X-ray microanalysis (EDX), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction analysis (XRD). The incorporation of a small amount (about 3 at. %) of both Pt and Ru into the SnO2-Sb electrodes produced a 400-times increase in their service life in alkaline medium, with no remarkable change in the electrocatalysis of the oxygen evolution reaction (OER). It is concluded that the deactivation of the electrodes is promoted by alkaline dissolution of metal species and coating detachment at high potentials. The introduction of Pt has a coating compacting effect, and Ru(IV), at low amounts until 9.75 at. %, replaces the Sn(IV) cations in the rutile-like SnO2 structure to form a solid solution that strongly increases the stability of the electrodes. The observed Ru segregation and decreased stability for larger Ru contents (x > 9.75 at. %), together with the selective dissolution of Ru after deactivation, suggest that the formation of a homogeneous (RuδSn1-δ)O2 single-phase is crucial for the stabilization of these electrodes.

Synthesis and Characterization of Three-Dimensional Porous Cu@Pt and Cu@Pt-Ru Catalysts for Methanol Oxidation

Highly porous Cu foams comprised of interconnected branched dendrites were used as sacrificial templates for the fabrication of pseudo core–shell Cu@Pt and Cu@Pt‐Ru unsupported electrodes by galvanic replacement. The as‐prepared materials presented a three‐dimensional structure with pores between 17 and 45 μm made of superimposed layers of ramified dendrites. TEM analysis showed that the dendrites were composed of agglomerates of grains of about 4 nm in size and mesopores of ca. 30 nm in diameter. The as‐prepared 3D electrodes were tested for methanol oxidation in acid media at different temperatures. The results showed that the catalytic activities of Cu@Pt and Cu@Pt‐Ru foams normalized to the electrochemical surface area are almost 50 % higher than that of a commercial Pt−Ru/C material, with poisoning rates that are reduced by half in the same potential range. The enhanced behavior of the as‐prepared foams is believed to be the result of the influence of copper atoms on the reactivity of platinum sites, the highly defective structure of the electrodes, as well as the facilitated diffusion of methanol molecules and the products formed during the reaction throughout the highly porous three‐dimensional structure of the electrode. The apparent activation energies (Ea,app) for the methanol oxidation reaction (MOR) were determined by potentiostatic experiments. Ea,app values of 29.07 and 24.20 kJ mol−1 were calculated for Cu@Pt and Cu@Pt‐Ru foams at 0.3 V, respectively. The results suggested that the MOR is governed by the dissociative adsorption of methanol as a result of the multifunctional nature of the catalyst and the facilitated diffusion of the products formed during the reaction.

Electroactive Mg2+-Hydroxyapatite Nanostructured Networks against Drug-Resistant Bone Infection Strains

Surface colonization competition between bacteria and host cells is one of the critical factors involved in tissue/implant integration. Current biomaterials are evaluated for their ability both of withstanding favorable responses of host tissue cells and of resisting bacterial contamination. In this work, the antibacterial ability of biocompatible Mg2+-substituted nanostructured hydroxyapatite (HA) was investigated. The densities of Staphylococcus aureus, Pseudomonas aeruginosa, and Escherichia coli strains were significantly decreased after culture in the presence of Mg-substituted HA materials in direct correlation with Mg2+-Ca2+ switch in the HA lattice. It was noticed that this decrease was accompanied by a minimal alteration of bacterial environments; therefore, the Mg2+-HA antibacterial effect was associated with the material surface topography and it electroactive behavior. It was observed that 2.23 wt % Mg2+-HA samples exhibited the best antibacterial performance; it decreased 2-fold the initial population of E. coli, P. aeruginosa, and S. aureus at the intermediate concentration (50 mg mL-1 of broth). Our results reinforce the potential of Mg-HA nanostructured materials to be used in antibacterial coatings for implantable devices and/or medicinal materials to prevent bone infection and to promote wound healing.

Efecto de aditivos orgánicos en la deposición de catalizadores Pt-Ru

The simultaneous codeposition of Pt and Ru on carbon materials was carried out potentiostatically at -0.5 V from H2PtCl6 and RuCl3 aqueous solutions in the presence of different organic additives: 1) ethylene glycol, 2) ethanol, 3) formic acid, 4) sodium citrate, 5) sodium tartrate and 6) Na2H2EDTA. The electrodeposition process was influenced thermodynamically and kinetically by the stabilizers. SEM and AFM analysis of the electrodes showed that both the particle size and the active surface area were notably affected by the presence of the stabilizing agents. The different behaviour of the stabilizing agents may be associated with the following effects: (1) the capability of the stabilizing agent to complex the metal ions, (2) the specific adsorption of organic molecules which inhibits particle growth, and (3) the reduction capability of the organic compounds. The electrodes prepared with different organic additives exhibit the following decreasing order of activities for methanol oxidation: citrate > tartrate > ethanol > Na2H2EDTA > ethylene glycol > formic acid > without stabilizer. This comportment can be related to differences in the active surface area, particle size and superficial structure of the metallic deposit.

Preparación electroquímica de electrodos bimetálicos PtRu soportados sobre sustratos carbonosos y su caracterización para la oxidación de metanol en medio ácido

In this work the influence of the electrochemical oxidation of different carbon substrates, such as glassy carbon, graphite cloth, graphite felt, and carbon fiber paper, on the electrodeposition of bimetallic PtRu catalysts was studied. The oxidation of the different substrates prior to the catalyst deposition, leads to remarkable improvement of catalyst dispersion, reduction of particle size and higher specific surface area of the catalyst, when was compared than that electrodes with the unnoxidized substrates. All the electrodes were used to study the methanol oxidation in acid media.