Porous carbonaceous materials simultaneously dispersing N, Fe and Co as bifunctional catalysts for the ORR and OER: electrochemical performance in a prototype of a Zn-air battery.

Infiltration of the mesoporous structure of SBA-15 silica as a hard template with phenanthroline complexes of Fe3+ and Co2+ allowed the simultaneous dispersion of nitrogen, iron and cobalt species on the surface of the obtained carbonaceous CMK-3 silica replica, with potential as bifunctional heterogeneous catalysts for the cathodic oxygen reduction and evolution reactions (ORR and OER). The textural properties and mesopore structure depended on the composition of the material. The carbonaceous FeCoNCMK-3 (1/1), obtained with an Fe/Co molar ratio of 1/1, exhibited an ordered cylindrical mesoporous structure with a high mesopore volume, a rather homogeneous composition in terms of total and surface concentrations of iron and cobalt, and a balanced presence of pyridinic-, pyrrolic- and graphitic-N species. FeCoNCMK-3 (1/1) could improve the ORR kinetics by adsorption and reduction of O2 through the 4-electron mechanism with a current density of -17.37 mA cm-2, Eonset of 1.13 V vs. RHE and E1/2 of 0.75 V when compared to metal-free, monometallic or bimetallic electrocatalysts with a higher amount of cobalt than that of iron. In addition, FeCoNCMK-3 (1/1) exhibited activity for the OER, presenting lower values of Eonset (1.52 V), Ej10 (1.78 V) and the Tafel slope (76.3 mV dec-1) with respect to other catalysts. When evaluated as a cathode in a prototype of a Zn-air battery, FeCoNCMK-3 (1/1) exhibited a high open circuit voltage of 1.41 V, a peak power density of 66.84 mW cm-2, a large specific capacity of 818.88 mA h gZn-1, and cycling for 20 h but with deactivation upon cycling.

Low Dispersity and High Conductivity Poly(4-styrenesulfonic acid) Membranes Obtained by Inexpensive Free Radical Polymerization of Sodium 4-styrenesulfonate.

Controlled polymerizations are often used to synthesize polymers with low dispersity, which involves expensive initiators, constrained atmospheres, and multi-step purifying processes, especially with water soluble monomers. These drawbacks make the synthesis very expensive and of little industrial value. In this report, an inexpensive free radical polymerization of sodium 4-styrenesulfonate, using benzoyl peroxide as initiator in water/N,N-dimethylformamide solutions, is presented. After polymerization, an easy fiber precipitation method is implemented to extract and purify the polymer, obtaining conversions up to 99%, recoveries up to 98%, and molecular weight dispersities in the range of 1.15⁻1.85, where the pseudo-controlled behavior is attributed to a thermodynamic limiting molecular weight solubility. Three different methods were used to bring the polymer to its acid form, obtaining Ion Exchange Capacities as high as 4.8 meq/g. Finally, polymeric membranes were prepared and reached conductivities up to 164 mS/cm, which makes them good candidates as proton exchange membranes in fuel cells.

Interplay between structure and dynamics in chitosan films investigated with solid-state NMR, dynamic mechanical analysis, and X-ray diffraction.

Modern solid-state NMR techniques, combined with X-ray diffraction, revealed the molecular origin of the difference in mechanical properties of self-associated chitosan films. Films cast from acidic aqueous solutions were compared before and after neutralization, and the role of the counterion (acetate vs Cl(-)) was investigated. There is a competition between local structure and long-range order. Hydrogen bonding gives good mechanical strength to neutralized films, which lack long-range organization. The long-range structure is better defined in films cast from acidic solutions in which strong electrostatic interactions cause rotational distortion around the chitosan chains. Plasticization by acetate counterions enhances long-range molecular organization and film flexibility. In contrast, Cl(-) counterions act as a defect and impair the long-range organization by immobilizing hydration water. Molecular motion and proton exchange are restricted, resulting in brittle films despite the high moisture content.

Síntesis y caratterización de fases estacionaris mesoporosas mediante pruebas cromatográficas y relaciones cuantitativas estructura-retención / Synthesis and characterization of mesoporous stationary phases using chromatographic tests and quantitative structure-retention relatinnships

En este trabajo se describe la síntesis, funcionalización y evaluación cromatográfica de tres sílicas mesoporosas con propiedades fisicoquímicas diferentes. Los materiales son preparados de acuerdo con métodos ya establecidos, que conducen a partículas isomórficas de tamaño micrométrico, y se modifican químicamente mediante un procedimiento clásico de silanización con octildimetilclorosilano seguido por silanización secundaria o end-capping con trimetilclorosilano. La prueba de Galushko y las relaciones cuantitativas estructura retención (RCER) son implementadas para la evaluación cromatográfica. Con el fin de realizar un estudio comparativo, los parámetros obtenidos se confrontan con los reportados en la literatura para cinco columnas comerciales. Aunque el comportamiento cromatográfico es el esperado para fases octil ligadas, los nuevos materiales presentan una mayor hidrofobicidad e inactividad química si se les compara con las columnas tradicionales. La asimetría observada para los picos es atribuida a irregularidades en el empaque debido a una mayor dispersión en el tamaño y la morfología de partícula.

In this work the synthesis, functionalization and chromatographic evaluation of three mesoporous silicas with different physical chemistry properties are described. The materials were prepared, as isomorphic micrometric particles, according to established methods and they were chemically modified by a classic procedure of silylation with octyldimethylchlorosilane followed by secondary silylation or end-capping. Galushko’ s test and quantitative structure-retention relationships were implemented for the chromatographic evaluation. A comparative study was done by comparing the parameters obtained with those reported in literature for five commercial columns. Although the chromatographic behavior is the expected for octyl phases, the new materials show larger hydrophobicity and chemical inactivity when compared with traditional columns. The asymmetric behavior of the peaks is attributed to packing irregularities due to a larger dispersion in particle size and morphology.