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Title: Below-Room-Temperature C–H Bond Breaking on an Inexpensive Metal Oxide: Methanol to Formaldehyde on CeO 2(111)

Abstract

C-H bond breaking is important for industrial commodity and specialty chemical transformations, including the upgrading of alcohols. Small primary alcohols – methanol and ethanol – are used industrially as precursors for the corresponding aldehydes at industrial scales. However, upgrading these primary alcohols involves C-H bond breaking and the processes are run at elevated temperatures (> 200 °C). In this work, new understanding from temperature programmed reaction (TPR) studies with methanol over a CeO 2(111) surface show the C-H bond breaking and the subsequent desorption of formaldehyde, even below room temperature. This is of particular interests because CeO 2 is a naturally abundant, inexpensive metal oxide. We combine density functional theory (DFT) and kinetic Monte Carlo (KMC) to simulate the TPR of methanol on CeO2. Our simulations show that the low temperature C H bond breaking occurs via disproportionation of adjacent methoxy species to form methanol and formaldehyde which each then desorb. We further show from DFT calculations that the same transition state with comparably low activation energies should be possible for other sustainable primary alcohols, with ethanol, 1-propanol, and 1-butanol having been explicitly calculated. In conclusion, these findings point out a new class of transition states to search for inmore » seeking low temperature C-H bond breaking over inexpensive metal oxides.« less

Authors:
ORCiD logo [1];  [2]; ORCiD logo [3]; ORCiD logo [1]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  2. Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States); Savannah River National Lab., Augusta, GA (United States)
  3. Univ. of Tennessee, Knoxville, TN (United States); Army Research Lab., Adelphi, MD (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1410920
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Physical Chemistry Letters
Additional Journal Information:
Journal Volume: 8; Journal ID: ISSN 1948-7185
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE

Citation Formats

Sutton, Jonathan E., Danielson, Thomas, Beste, Ariana, and Savara, Aditya Ashi. Below-Room-Temperature C–H Bond Breaking on an Inexpensive Metal Oxide: Methanol to Formaldehyde on CeO2(111). United States: N. p., 2017. Web. doi:10.1021/acs.jpclett.7b02683.
Sutton, Jonathan E., Danielson, Thomas, Beste, Ariana, & Savara, Aditya Ashi. Below-Room-Temperature C–H Bond Breaking on an Inexpensive Metal Oxide: Methanol to Formaldehyde on CeO2(111). United States. doi:10.1021/acs.jpclett.7b02683.
Sutton, Jonathan E., Danielson, Thomas, Beste, Ariana, and Savara, Aditya Ashi. Tue . "Below-Room-Temperature C–H Bond Breaking on an Inexpensive Metal Oxide: Methanol to Formaldehyde on CeO2(111)". United States. doi:10.1021/acs.jpclett.7b02683. https://www.osti.gov/servlets/purl/1410920.
@article{osti_1410920,
title = {Below-Room-Temperature C–H Bond Breaking on an Inexpensive Metal Oxide: Methanol to Formaldehyde on CeO2(111)},
author = {Sutton, Jonathan E. and Danielson, Thomas and Beste, Ariana and Savara, Aditya Ashi},
abstractNote = {C-H bond breaking is important for industrial commodity and specialty chemical transformations, including the upgrading of alcohols. Small primary alcohols – methanol and ethanol – are used industrially as precursors for the corresponding aldehydes at industrial scales. However, upgrading these primary alcohols involves C-H bond breaking and the processes are run at elevated temperatures (> 200 °C). In this work, new understanding from temperature programmed reaction (TPR) studies with methanol over a CeO2(111) surface show the C-H bond breaking and the subsequent desorption of formaldehyde, even below room temperature. This is of particular interests because CeO2 is a naturally abundant, inexpensive metal oxide. We combine density functional theory (DFT) and kinetic Monte Carlo (KMC) to simulate the TPR of methanol on CeO2. Our simulations show that the low temperature C H bond breaking occurs via disproportionation of adjacent methoxy species to form methanol and formaldehyde which each then desorb. We further show from DFT calculations that the same transition state with comparably low activation energies should be possible for other sustainable primary alcohols, with ethanol, 1-propanol, and 1-butanol having been explicitly calculated. In conclusion, these findings point out a new class of transition states to search for in seeking low temperature C-H bond breaking over inexpensive metal oxides.},
doi = {10.1021/acs.jpclett.7b02683},
journal = {Journal of Physical Chemistry Letters},
issn = {1948-7185},
number = ,
volume = 8,
place = {United States},
year = {2017},
month = {11}
}

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