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Abstract:
The solid fullerenes C60 and C70 react in deliberate and adventitious situations with molecular oxygen in a wide range of temperatures. Using thin films and polycrystalline bulk samples with well-defined structures and chemical histories we investigated the complex process from molecular intercalation over atomic adduct formation to deep oxidation and polymerisation which together describe the oxidation reaction. A combination of photoemission (UPS, XPS) photoabsorption (XAS), FT-IR, temperature-programmed and isothermal gravimetric measurements and DSC allowed to identify the existence and gradual interconversion of the three types of solid products besides the gas phase products CO and CO2. Both fullerenes react along the same reaction path. The difference of the molecular structures results in different activation barriers in the initial step of intercalation and in the final step of cage-opening. The overall reactivity of both fiiHerenes is quite similar at temperatures above the gasification onset of 570 K. The formation of the various adduct compounds was found to exert a detectable influence upon the overall molecular shape of the fiiHerenes and a small effect on the electronic structure was observed. The only moderate differences in electronic and geometric structures of pristine and initially oxidised fullerenes precludes a pronounced molecule-by-molecule reaction control and allows the topochemistry of the intercalation to control the shape of the reaction interface. This control is less effective for C70 than for the C60 fullerene.
