An electrodeposition method based on chronoamperometry was used to develop a highly reproducible and fast elaboration method of adherent manganese dioxide thin films on a glassy carbon electrode from aqueous solutions containing sulfuric acid and manganese sulfate. The resulting films were found to have a nanostructured character presumably due rather to birnessite (G-MnO 2) than to J-MnO 2 , as suggested by their Raman and XRD signatures. They lead to modified electrodes that present an obvious although complex pH dependent potentiometric response. This sensor indeed showed a single slope non-Nernstian linear behaviour over the 1.5-12 pH range for increasing pH direction ("trace") whereas a Nernstian two slopes linear behaviour was observed for decreasing pH direction ("re-trace"). Preliminary EIS experiments carried out at a pH value of 1.8 seem to reveal a sensitivity mechanism based on proton insertion process at least at highly acidic pH values.
International audienceIn this investigation, Mn3O4 spinel-type oxide was synthesized at low temperature using the Pechini process. We employed a sol-gel route, in which a solution of Mn(II) in a mixture of citric acid and ethylene glycol was heated to form a polymeric precursor, followed by annealing at lower temperature. The oxide obtained was identified by X-ray diffraction, scanning electron spectroscopy, and Raman spectroscopy. The results revealed that the formation of Mn3O4 hausmannite structure with a minor secondary phase of MnSO4 occurred at or above 280 A degrees C. The sample powder consisted of fine grains with homogeneous morphology and an average size close to 1 mu m was obtained. This new preparation procedure yielded an electrode oxide which appears to be a promising cathode material for fuel cells and metal-air batteries
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