Decomposition of Furan on Pd(111)

Xu, Ye

doi:10.1007/s11244-012-9797-z

Title: Decomposition of Furan on Pd(111)

Journal Article · Sun Jan 01 00:00:00 EST 2012 · Topics in Catalysis

DOI:https://doi.org/10.1007/s11244-012-9797-z· OSTI ID:1040749

Xu, Ye ^[1]

ORNL

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{sub a} = 0.82 eV, which yields a C{sub 4}H{sub 4}O aldehyde species that rapidly loses the {alpha} H to form C{sub 4}H{sub 3}O (E{sub a} = 0.40 eV). C{sub 4}H{sub 3}O further dehydrogenates at the {delta} position to form C{sub 4}H{sub 2}O (E{sub a} = 0.83 eV), before the {alpha}-{beta} C-C bond dissociates (E{sub 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 C{sub 4}H{sub 2}O intermediate delays the decarbonylation step up to 350 K.

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Research Organization:: Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)

Sponsoring Organization:: USDOE Office of Science (SC)

DOE Contract Number:: DE-AC05-00OR22725

OSTI ID:: 1040749

Journal Information:: Topics in Catalysis, Vol. 55, Issue 5-6; ISSN 1022-5528

Country of Publication:: United States

Language:: English

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