Abstract
The electronic features determining the reactivity of CO and CH X on transition metal surfaces are reviewed. Focus is on the relevant features that control the Fischer-Tropsch synthesis. The CO dissociation reaction path is controlled by the interaction with the CO bond strength weakening 2π* orbitals. CH3 fragment adsorption is controlled by σ type molecule fragment orbitals. This directs the CH3 fragment to the atop adsorption site on those late transition metals that have strongly interacting d-valence electrons. Adsorbed C and O have a stronger bond strength than CH3 because they have also unoccupied atomic p orbitals available to bonding. Because the bond strength of adsorbed C and O increases more rapidly with depletion of d-valence electron occupation than that of CO, the activation energy for CO dissociation decreases for the corresponding transition metals towards the left of the periodic system. The rate of methanation versus chain growth is controlled by the strength of the M-CH3 bond versus the activation energy of carbon-carbon bond formation. The first appears to be more sensitive to variations in metal carbon bond strength than the latter.
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Van Santen, R.A., De Koster, A. & Koerts, T. The quantum chemical basis of the Fischer-Tropsch reaction. Catal Lett 7, 1–14 (1990). https://doi.org/10.1007/BF00764488
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DOI: https://doi.org/10.1007/BF00764488