Structures, physicochemical properties and oxygen reduction activities of carbons derived from ferrocene-poly(furfuryl alcohol) mixtures
The structure, physicochemical properties and oxygen reduction abilities of carbons prepared by the carbonization of mixtures of ferrocene and poly(furfuryl alcohol) were studied. X-ray diffraction (XRD), Raman spectroscopy and transmission electron microscopy (TEM) studies revealed that the carbons thus prepared consisted of two components; amorphous and turbostratic shell-like components. The fraction, f sharp, obtained by the analysis of the (002) peak in XRD was found to be a parameter that represented the degree of formation of the shell-like components. The formation of the shell-like components induced an increase in the mesopore volumes. Electrical conductivity increased exponentially with f sharp, which indicated that the conduction process was governed by a percolation process of the conductive shell-like components. The amount of CO-desorption by O2-TPD technique showed a maximum desorption at f sharp=0.3, and the further development in the sharp component led to a decrease in the CO-desorption. Mössbauer spectroscopy technique revealed the presence of α-Fe, γ-Fe, Fe1-x O and Fe3C in the prepared carbons, which were soluble species to acids. The oxygen reduction activity was studied in a oxygen saturated sulfuric acid solution by rotating disk electrode voltammetry. The oxygen reduction potential varied with f sharp; initially it increased by f sharp=0.3 and then it decreased at higher f sharp values. This behavior was similar to that of CO-desorption, which meant the presence of an adequate degree of the development of the shell-like structure for maximizing oxygen adsorption. Removal of the surface metal component from the carbons by acid-washing resulted in no decrease in the oxygen reduction activities of the carbons. The nature of the active sites on the carbon materials is discussed.
Keywordscatalytic carbonization ferrocene oxygen reduction poly(furfuryl alcohol) shell-like carbon turbostratic carbon
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This study was conducted as a project of the Research and Development of Polymer Electrolyte Fuel Cell, entrusted by the New Energy and Industrial Technology Development Organization (NEDO), (2002–2004 fiscal years). LJB and JDC received a grant from the Australian Research Council to conduct the Mössbauer measurements.
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