Theoretical calculation of the dehydrogenation of ethanol on a Rh/CeChO2(111) surface

Hui Lung Chen, Shih Hung Liu, Jia Jen Ho

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Abstract

We applied periodic density-functional theory (DFT) to investigate the dehydrogenation of ethanol on a Rh/ CeO2 (111) surface. Ethanol is calculated to have the greatest energy of adsorption when the oxygen atom of the molecule is adsorbed onto a Ce atom in the surface, relative to other surface atoms (Rh or O). Before forming a six-membered ring of an oxametallacyclic compound (Rh-CH2CH2O-Ce(a)), two hydrogen atoms from ethanol are first eliminated; the barriers for dissociation of the O-H and the β-carbon (CH2-H) hydrogens are calculated to be 12.00 and 28.57 kcal/mol, respectively. The dehydrogenated H atom has the greatest adsorption energy (Eads = 101.59 kcal/mol) when it is adsorbed onto an oxygen atom of the surface. The dehydrogenation continues with the loss of two hydrogens from the α-carbon, forming an intermediate species Rh-CH2CO-Ce(a), for which the successive barriers are 34.26 and 40.84 kcal/mol. Scission of the C-C bond occurs at this stage with a dissociation barrier Ea = 49.54 kcal/mol, to form Rh-CH2(a) + 4H(a) + CO(g). At high temperatures, these adsorbates desorb to yield the final products CH 4(g), H2(g), and CO(g).

Original languageEnglish
Pages (from-to)14816-14823
Number of pages8
JournalJournal of Physical Chemistry B
Volume110
Issue number30
DOIs
Publication statusPublished - 2006 Aug 3

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ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films
  • Materials Chemistry

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