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Title: Methyl Formate Formation during Methanol Conversion over the (111) Ceria Surface

Abstract

We study methyl formate formation during methanol conversion on the fully oxidized and partially reduced ceria (111) surface using density functional theory. Starting from methanol and formaldehyde adsorbed on the surface, we consider two pathways of methyl formate production. Pathway 1 consists of formaldehyde dehydrogenation followed by oxygen–carbon bond formation. Along pathway 2, the oxygen–carbon bond is established prior to intermediate dehydrogenation. Formaldehyde production is observed at elevated temperature at which we expect both pathways to be energetically attainable on the fully oxidized surface. However, the probability of both reactants being adsorbed next to each other is low. This probability can be increased by the reduction of the surface. The partially reduced ceria surface is modeled by the introduction of an oxygen vacancy in the surface. If formaldehyde adsorbs over a vacancy, both pathways potentially contribute to methyl formate formation. In contrast, if methoxide that is obtained by dissociative adsorption of methanol is placed in the vacancy, methyl formate production becomes energetically highly demanding. Still, dehydrogenation of methoxide or methoxide exchange with coadsorbates converts methoxide in a vacancy to an active species for methyl formate formation while increasing the residence time of methoxide on the surface. Importantly, the preference ofmore » pathway 1 is due to the promotion of surface-bound formaldehyde dehydrogenation by methoxide.« less

Authors:
ORCiD logo [1]; ORCiD logo [2]
  1. Univ. of Tennessee, Oak Ridge, TN (United States). Joint Inst. for Computational Sciences,
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1480467
Alternate Identifier(s):
OSTI ID: 1607320
Grant/Contract Number:  
AC02-05CH11231; AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 121; Journal Issue: 18; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Beste, Ariana, and Overbury, Steven H. Methyl Formate Formation during Methanol Conversion over the (111) Ceria Surface. United States: N. p., 2017. Web. https://doi.org/10.1021/acs.jpcc.7b01431.
Beste, Ariana, & Overbury, Steven H. Methyl Formate Formation during Methanol Conversion over the (111) Ceria Surface. United States. https://doi.org/10.1021/acs.jpcc.7b01431
Beste, Ariana, and Overbury, Steven H. Tue . "Methyl Formate Formation during Methanol Conversion over the (111) Ceria Surface". United States. https://doi.org/10.1021/acs.jpcc.7b01431. https://www.osti.gov/servlets/purl/1480467.
@article{osti_1480467,
title = {Methyl Formate Formation during Methanol Conversion over the (111) Ceria Surface},
author = {Beste, Ariana and Overbury, Steven H.},
abstractNote = {We study methyl formate formation during methanol conversion on the fully oxidized and partially reduced ceria (111) surface using density functional theory. Starting from methanol and formaldehyde adsorbed on the surface, we consider two pathways of methyl formate production. Pathway 1 consists of formaldehyde dehydrogenation followed by oxygen–carbon bond formation. Along pathway 2, the oxygen–carbon bond is established prior to intermediate dehydrogenation. Formaldehyde production is observed at elevated temperature at which we expect both pathways to be energetically attainable on the fully oxidized surface. However, the probability of both reactants being adsorbed next to each other is low. This probability can be increased by the reduction of the surface. The partially reduced ceria surface is modeled by the introduction of an oxygen vacancy in the surface. If formaldehyde adsorbs over a vacancy, both pathways potentially contribute to methyl formate formation. In contrast, if methoxide that is obtained by dissociative adsorption of methanol is placed in the vacancy, methyl formate production becomes energetically highly demanding. Still, dehydrogenation of methoxide or methoxide exchange with coadsorbates converts methoxide in a vacancy to an active species for methyl formate formation while increasing the residence time of methoxide on the surface. Importantly, the preference of pathway 1 is due to the promotion of surface-bound formaldehyde dehydrogenation by methoxide.},
doi = {10.1021/acs.jpcc.7b01431},
journal = {Journal of Physical Chemistry. C},
number = 18,
volume = 121,
place = {United States},
year = {2017},
month = {5}
}

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Figures / Tables:

Figure 1 Figure 1: Reaction pathways to form methyl formate over ceria considered in this work.

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Works referencing / citing this record:

Exploring the methanol decomposition mechanism on the Pt 3 Ni(100) surface: a periodic density functional theory study
journal, January 2018

  • Du, Pan; Gao, Yuan; Wu, Ping
  • Physical Chemistry Chemical Physics, Vol. 20, Issue 15
  • DOI: 10.1039/c8cp00768c

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