Abstract
Periodic density functional theory calculations (GGA-PBE) have been performed to investigate the mechanism for the decomposition of furan up to CO formation on the Pd(111) surface. At 1/9 ML coverage, furan adsorbs with its molecular plane parallel to the surface in several states with nearly identical adsorption energies of −1.0 eV. The decomposition of furan begins with the opening of the ring at the C–O position with an activation barrier of E a = 0.82 eV, which yields a C4H4O aldehyde species that rapidly loses the α H to form C4H3O (E a = 0.40 eV). C4H3O further dehydrogenates at the δ position to form C4H2O (E a = 0.83 eV), before the α–β C–C bond dissociates (E a = 1.08 eV) to form CO. Each step is the lowest-barrier dissociation step in the respective species. A simple kinetic analysis suggests that furan decomposition begins at 240–270 K and is mostly complete by 320 K, in close agreement with previous experiments. It is suggested that the C4H2O intermediate delays the decarbonylation step up to 350 K.
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Acknowledgments
This work was performed at the Center for Nanophase Materials Sciences, which is sponsored at Oak Ridge National Laboratory by the Division of Scientific User Facilities, U.S. Department of Energy (DOE), and used resources of the National Energy Research Scientific Computing Center, which is supported by DOE Office of Science under Contract DE-AC02-05CH11231, and resources of the Oak Ridge Leadership Computing Facility, which is supported by DOE Office of Science under Contract DE-AC05-00OR22725. I thank Dr. Aditya Ashi Savara for helpful discussions.
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Xu, Y. Decomposition of Furan on Pd(111). Top Catal 55, 290–299 (2012). https://doi.org/10.1007/s11244-012-9797-z
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DOI: https://doi.org/10.1007/s11244-012-9797-z