Abstract

The adsorption of the C2 hydrocarbons, including ethane, ethene, and ethyne, are studied on magnetite Fe3O4(001) by a combination of molecular beam dosing, temperature programmed desorption, and X-ray photoelectron spectroscopy. The ethane desorption profile has a single temperature invariant peak at 100 K, while ethene and ethyne exhibit additional peaks at ∼120 -and ∼135 K. An inversion analysis is used to extract coverage-dependent desorption energies as well as coverage-averaged prefactors for each molecule. Ethene and ethyne exhibit moderate coverage-dependent desorption energies decreasing from ∼80 to ∼30 kJ/mol at saturation, while ethane shows a relatively coverage invariant desorption energy ∼28 kJ/mol. The desorption energies of the C2 hydrocarbons increase in the order of increasing bond order. This is likely due to the enhanced interaction of the ethene and ethyne π system to the coordinatively unsaturated octahedral Fe sites (Feoct) on the oxide surface. The saturation coverages of each C2 hydrocarbon at 82 K were also determined. These match well with the 2-dimensional area determined from their liquid densities.

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