Coadsorbed Species Explain the Mechanism of Methanol Temperature-Programmed Desorption on CeO2(111)

Sutton, Jonathan E.; Overbury, Steven H.; Beste, Ariana

doi:10.1021/acs.jpcc.6b02128

Title: Coadsorbed Species Explain the Mechanism of Methanol Temperature-Programmed Desorption on CeO₂(111)

Journal Article · Thu Mar 24 00:00:00 EDT 2016 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.6b02128· OSTI ID:1250415

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

Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Computer Science and Mathematics Division

Here, we have used density functional theory calculations to investigate the temperature-programmed desorption (TPD) of methanol from CeO₂(111). For the first time, low-temperature water formation and high-temperature methanol desorption are explained by our calculations. High coverages of methanol, which correspond to experimental conditions, are required to properly describe these features of the TPD spectrum. We identify a mechanism for the low-temperature formation of water involving the dissociation of two methanol molecules on the same surface O atom and filling of the resulting surface vacancy with one of the methoxy products. After water desorption, methoxy groups are stabilized on the surface and react at higher temperatures to form methanol and formaldehyde by a disproportionation mechanism. Alternatively, the stabilized methoxy groups undergo sequential C–H scission reactions to produce formaldehyde. Calculated energy requirements and methanol/formaldehyde selectivity agree with the experimental data.

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Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF)

Sponsoring Organization:: DOE Office of Science (SC); USDOE

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1250415

Journal Information:: Journal of Physical Chemistry. C, Vol. 120, Issue 13; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 13 works

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