Dehydrogenation of methanol to formaldehyde catalyzed by pristine and defective ceria surfaces

Beste, Ariana; Overbury, Steven H.

doi:10.1039/C6CP00151C

Title: Dehydrogenation of methanol to formaldehyde catalyzed by pristine and defective ceria surfaces

Journal Article · Tue Mar 08 23:00:00 EST 2016 · Physical Chemistry Chemical Physics. PCCP

DOI: https://doi.org/10.1039/C6CP00151C · OSTI ID:1248781

Beste, Ariana ^[1]; Overbury, Steven H. ^[2]

Joint Institute for Computational Sciences, The Univ. of Tennessee, Oak Ridge (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science (CNMS)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division

We have explored the dehydrogenation of methoxy on pristine and defective (111), (100), and (110) ceria surfaces with density functional methods. Methanol conversion is used as a probe reaction to understand structure sensitivity of the oxide catalysis. Differences in reaction selectivity have been observed experimentally as a function of crystallographically exposed faces and degree of reduction. We find that the barrier for carbon-hydrogen cleavage in methoxy is similar for the pristine and defective (111), (100), and (110) surfaces. However, there are large differences in the stability of the surface intermediates on the different surfaces. The variations in experimentally observed product selectivities are a consequence of the interplay between barrier controlled bond cleavage and desorption processes. Ultimately, subtle differences in activation energies for carbon-hydrogen cleavage on the different crystallographic faces of ceria could not be correlated with structural or electronic descriptors.

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Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC05-00OR22725; AC02-05CH11231

OSTI ID:: 1248781

Journal Information:: Physical Chemistry Chemical Physics. PCCP, Journal Name: Physical Chemistry Chemical Physics. PCCP Journal Issue: 15 Vol. 18; ISSN 1463-9076; ISSN PPCPFQ

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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