RESUMEN
The Li+ ion mobility through the porous cathode is a critical aspect in the development of commercial Li-air batteries. The bulk transport properties of lithium salts in organic solvents are not reliable parameters for the design of this type of battery since confinement could significantly modify the transport properties, especially when pore diameters are below 10 nm. In this work, we studied the effect of the carbon mesostructure and surface charge on the diffusion of LiTf and LiTFSI salts dissolved in diglyme, typical electrolytes for lithium-air batteries. Interdiffusion coefficients of the salts were determined using a conductimetric method. NMR spectroscopy and relaxometry were used to explore the effect of the carbon structure and the surface charge density on the interaction between the electrolytes and the pore wall. We showed that carbon micro/mesoporous structure plays a critical role in the transport properties of the electrolyte, producing a decrease of up to 2-3 orders of magnitude in the salt interdiffusion coefficients when going from bulk solutions to pores below 4 nm in diameter. It was observed that for pores 25 nm in diameter, the reduction in the diffusion coefficient can be mainly ascribed to the porosity of the sample, giving tortuosity factors around 1. However, for smaller pore sizes (1-10 nm diameter) bigger tortuosity coefficients were observed and were related to strong ion-pore wall interactions. Moreover, it was noticed that the ratio between the diffusion coefficients of the two studied salts dissolved in diglyme, is different in bulk and under confinement, demonstrating that the interactions of the ions with the charged pore wall probably compete with the cation-anion interactions, affecting salt association under confinement.
RESUMEN
With the goal of improving the mechanical properties of porous hierarchical carbon, cellulosic fiber fabric was incorporated into the resorcinol/formaldehyde (RF) precursor resins. The composites were carbonized in an inert atmosphere, and the carbonization process was monitored by TGA/MS. The mechanical properties, evaluated by nanoindentation, show an increase in the elastic modulus due to the reinforcing effect of the carbonized fiber fabric. It was found that the adsorption of the RF resin precursor onto the fabric stabilizes its porosity (micro and mesopores) during drying while incorporating macropores. The textural properties are evaluated by N2 adsorption isotherm, which shows a surface area (BET) of 558 m2g-1. The electrochemical properties of the porous carbon are evaluated by cyclic voltammetry (CV), chronocoulometry (CC), and electrochemical impedance spectroscopy (EIS). Specific capacitances (in 1 M H2SO4) of up to 182 Fg-1 (CV) and 160 Fg-1 (EIS) are measured. The potential-driven ion exchange was evaluated using Probe Bean Deflection techniques. It is observed that ions (protons) are expulsed upon oxidation in acid media by the oxidation of hydroquinone moieties present on the carbon surface. In neutral media, when the potential is varied from values negative to positive of the potential of zero charge, cation release, followed by anion insertion, is found.
RESUMEN
Mesoporous carbons (MCs) with different pore sizes were synthesized and evaluated as a catalyst support for fuel cells. The MCs were obtained from resorcinol-formaldehyde precursors, polymerized in the presence of polydiallyldimethylammonium chloride (cationic polyelectrolyte) as a structuring agent and commercial silica (Sipernat® or Aerosil®) as the hard template. The MC obtained with Aerosil® shows a broad pore size distribution with a maximum at 21 nm. On the other hand, the MCs with Sipernat® show a bimodal pore size distribution, with a narrow peak centered at 5 nm and a broad peak with a maximum ca. 30 nm. All MCs present a high specific surface area (800-1000 m2 g-1) and total pore volume ranging from 1.36 to 1.69 cm3 g-1. PtRu nanoparticles were deposited onto the MC support by an impregnation-reduction method with NaBH4 at 80 °C in basic media. The electrochemical characterization reveals improved electrocatalysis towards the methanol oxidation for the catalyst deposited over the carbon with the highest total pore volume. This catalyst also presented the highest CO2 conversion efficiency, ca. 80%, for the methanol oxidation as determined by differential electrochemical mass spectroscopy analysis. Moreover, the catalyst as a fuel cell anode showed the best performance, reaching a power density of 125 mW cm-2 at 90 °C with methanol as fuel and dry O2.
RESUMEN
Gold nanoparticles (NP) trapped in the mesopores of mixed zirconia-ceria thin films are prepared in a straightforward and reproducible way. The films exhibit enhanced stability and excellent catalytic activity in nitro-group reduction by borohydride and electrocatalytic activity in CO and ethanol oxidation and oxygen reduction.
RESUMEN
High activity mesoporous Pt/Ru catalysts with 2D-hexagonal structure were synthesized using a triblock poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) copolymer (Pluronic F127) template. The normalized mass activities for the methanol oxidation reaction (MOR) of the Pt/Ru catalysts with a regular array of pores is higher than those reported for nanoparticulated Pt/Ru catalysts. Different kinetic parameters, as Tafel slope and activation energy, were obtained for the MOR on the mesoporous catalysts. Results indicated that catalysts performance depends on pore size. Mass activities and the CO2 conversion efficiency for large pore size mesoporous catalysts (10 nm) are greater than those reported for smaller pore size mesoporous catalysts with similar composition. The effect of pore size on catalysts performance is related to the greater accessibility of methanol to the active areas inside large pores. Consequently, the overall residence time of methanol increases as compared with mesoporous catalyst with small pores.
RESUMEN
Highly porous carbon composites, suitable to be used as electrodes in electrochemical double layer capacitors, could be produced by pyrolysis of resorcinol-formaldehyde resins impregnated onto a natural fibre material (celullosic fabric), without additional template agents or special drying of the polymer gels.