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Adsorption energies and prefactor determination for CH3OH adsorption on graphite

par webmaster - publié le , mis à jour le

In this paper, we have studied adsorption and thermal desorption of methanol CH3OH on graphite surface, with the specific aim to derive from experimental data quantitative parameters that govern the desorption, namely, adsorption energy Eads and prefactor ν of the Polanyi-Wigner law. In low coverage regime, these two values are interconnected and usually the experiments can be reproduced with any couple (Eads, ν), which makes intercomparison between studies difficult since the results depend on the extraction method.

Here, we use a method for determining independently the average adsorption energy and a prefactor value that works over a large range of incident methanol coverage, from a limited set of desorption curves performed at different heating rates. In the low coverage regime the procedure is based on a first order kinetic law, and considers an adsorption energy distribution which is not expected to vary with the applied heating rate.

In the case of CH3OH multilayers, Eads is determined as 430 meV with a prefactor of 5 × 1014 s−1. For CH3OH submonolayers on graphite, adsorption energy of 470 ± 30 meV and a prefactor of (8 ± 3) × 1016 s−1 have been found. These last values, which do not change between 0.09 ML and 1 ML initial coverage, suggest that the methanol molecules form island-like structure on the graphite even at low coverage.

Journal : J Chem Phys 143, 084703 (2015) JCP