We investigated the crystalline phase and electronic structure of perovskite-type La1-xSrxMnO3 (0.0 ≤ x ≤ 1.0) (LSMx) catalysts synthesized via the citric sol-gel route, for H2O2 reduction. The resulting materials were characterized by XRD, XANES, TR-XANES, and TPO and, after calcination, consisted of cubic perovskite for 0.0 ≤ x ≤ 0.8 and hexagonal perovskite for x = 1.0. Mn species in the precalcined catalysts were oxidized to Mn(3+) for x = 0.0 to 0.6 and to Mn(2+) for x = 0.8 and 1.0. After calcination, Mn species were present in a mixed oxidation state of Mn(3+)/Mn(4+), while Sr(2+) and La(3+) were not altered. TR-XANES and TPO showed that Mn species were oxidized at 210-220 °C and formed active perovskites LSM0.4 and LSM0.0 at 580 °C and 640 °C. This shows that Sr doping can reduce the oxidation temperature of LSMx with 0.2 ≤ x ≤ 0.4. However, the concentration of Mn(4+) in LSMx is increased which is useful for enhancing their catalytic activity and stability. When tested in an alkaline electrolyte, LSM0.6 containing the optimum Mn(4+)/Mn(3+) ratio promoted the formation of hydroxyl via the oxygen intercalation reaction and exhibited low polarization resistance and the highest catalytic activity for H2O2 reduction.
A direct-methanol fuel cell containing three parts: microchannels, electrodes, and a proton exchange membrane (PEM), was investigated. Nafion resin (NR) and polystyrene-block-poly(ethylene-ran-butylene)-block-polystyrene (PS) were used as PEMs. Preparation of PEMs, including compositing with other polymers and their solubility, was performed and their proton conductivity was measured by a four point probe. The results showed that the 5 % Nafion resin has lower conductivity than the 5 % PS solution. The micro-fuel cell contained two acrylic channels, PEM, and two platinum catalyst electrodes on a silicon wafer. The assembled micro-fuel cells used 2 M methanol at the flow rate of 1.5 mL min−1 in the anode channel and 5 × 10−3 M KMnO4 at the flow rate of 1.5 mL min−1 in the cathode channel. The micro-fuel cell with the electrode distance of 300 μm provided the power density of 59.16 μW cm−2 and the current density of 125.60 μA cm−2 at 0.47 V.
PdCoNi nanocomposites supported on graphene (PdCoNi/G) have been obtained from chemical reduction of metal catalysts and graphite oxide (GO) with a strong reducing agent, followed by calcination at high temperature under N2 condition, and used for electrooxidation of methanol in direct methanol fuel cell. The morphologies and structural properties of electrocatalysts were examined by scanning electron microscopy (SEM) and X-ray diffraction (XRD). X-ray spectroscopy techniques (X-ray photoelectron spectroscopy XPS) was used to investigate the chemical state of the synthesized catalysts. The results of Pd XPS spectra showed the metallic Pd and PdO phases for precalcined and calcined PdCoNi/G nanocomposite, respectively. The X-ray measurement of Co and Ni displayed the various metallic oxides in synthesized electrocatalysts. For electrochemical analysis, cyclic voltammetry (CV) and chronoamperometry (CA) indicated that the PdCoNi/G nanocomposites enhanced the methanol oxidation, compared to the lower activity in the calcined electrocatalysts.
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