Oxygen reduction reaction catalyzed by epsilon-MnO2: Influence of the crystalline structure on the reaction mechanism

The oxygen reduction reaction (ORR) was studied in KOH electrolyte on carbon supported epsilon-manganese dioxide (epsilon-MnO2/C). The epsilon-MnO2/C catalyst was prepared via thermal decomposition of manganese nitrate and carbon powder (Vulcan XC-72) mixtures. X-ray powder diffraction (XRD) measurements were performed in order to determine the crystalline structure of the resulting composite, while energy dispersive X-ray analysis (EDX) was used to evaluate the chemical composition of the synthesized material. The electrochemical studies were conducted using cyclic voltammetry (CV) and quasi-steady state polarization measurements carried out with an ultra thin layer rotating ring/disk electrode (RRDE) configuration. The electrocatalytic results obtained for 20% (w/w) Pt/C (E-TEK Inc., USA) and alpha-MnO2/C for the ORR, considered as one of the most active manganese oxide based catalyst for the ORR in alkaline media, were included for comparison. The RRDE results revealed that the ORR on the MnO2 catalysts proceeds preferentially through the complete 4e(-) reduction pathway via a 2 plus 2e(-) reduction process involving hydrogen peroxide as an intermediate. A benchmark close to the performance of 20% (w/w) Pt/C (E-TEK Inc., USA) was observed for the epsilon-MnO2/C material in the kinetic control region, superior to the performance of alpha-MnO2/C, but a higher amount of HO2- was obtained when epsilon-MnO2/C was used as catalyst. The higher production of hydrogen peroxide on epsilon-MnO2/C was related to the presence of structural defects, typical of this oxide, while the better catalytic performance in the kinetic control region compared to alpha-MnO2/C was related with the higher electrochemical activity for the proton insertion kinetics, which is a structure sensitive process. (C) 2012 Elsevier Ltd. All rights reserved.

Nanogravimetric study of lead underpotential deposition on selenium thin films as a semiconductor alloy formation procedure

An electrochemical quartz crystal microbalance Au electrode modified with a Se thin film was used to investigate the electrochemical behavior of lead ad-atoms using underpotential deposition (UPD) conditions. A specific quasi-reversible process was observed during the reduction of Pb2+ on Se thin films in perchloric acid media. The charge density of Pb ad-atoms on Se thin film (46.86 mu C cm(-2)) suggests a recovery of 0.1 monolayers, which is in good agreement with EQCM data. The Se thin film can be successfully alloyed with Pb atoms that are deposited by chronoamperometry using time intervals large enough to allow for diffusion toward the inner Se phase. Linear sweep voltammetry combined with EQCM in perchloric acid was used to characterize the amount of Pb absorbed in the Se thin film. These findings offer a new strategy for alloy formation in semiconductor films using UPD as an effective tool to quantify the exact amount of the incorporated metal.

Dynamical Elastic Moduli of the Ti-13Nb-13Zr biomaterial alloy by mechanical spectroscopy

Dynamical Elastic Moduli of the Ti-13Nb-13Zr biomaterial alloy were obtained using the mechanical spectroscopy technique. The sample with heat treatment at 1170K for 30 minutes and water quenched with subsequent aging treatment at 670 K for 3 hours (TNZ + WQ + 670 K/3 h), was characterized through decay of free oscillations of the sample in the flexural vibration mode. The spectra of anelastic relaxation (internal friction and frequency) in the temperature range from 300 K to 625 K not revealed the presence of relaxation process. As shown in the literature, the hcp structure usually does not exhibit any relaxation due to the symmetry of the sites in the crystalline lattice, but if there is some relaxation, this only occurs in special cases such as low concentration of zirconium or saturation of the stoichiometric ratio of oxygen for zirconium. Dynamical elastic modulus obtained for TNZ + WQ + 670 K/3 h alloy was 87 GPa at room temperature, which is higher than the value for Ti-13Nb-13Zr alloy (64 GPa) of the literature. This increment may be related to the change of the proportion of α and β phases. Besides that, the presence of precipitates in the alloy after aging treatment hardens the material and reduces its ductility.