Abstract
The thermal decomposition of the three dodecacarbonyl clusters, Fe 3(CO) 12, Ru 3(CO) 12 and Os 3(CO) 12, on a clean carbon surface has been monitored by DRIFTS (Diffuse Reflectance Fourier Transform Infrared Spectroscopy) at different temperatures under a He or H 2 atmosphere. First-order rate constants and activation energies were determined. Different intermediate species were observed, and the absence of oxygen species on the surface allowed the formation of zero-valent metal particles during decomposition. The subsequent highly dispersed, carbon-supported metal catalysts have been characterized by the calorimetric measurement of the heats of adsorption of CO and by their kinetic behavior in the CO hydrogenation reaction. The CO heats of adsorption and the activation energies for both decarbonylation and methanation showed the same trend among the clusters as the initial metal-CO bond strengths.
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