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Title: Methanol partial oxidation on Ag(111) from first principles

Abstract

In this work, we examine the thermochemistry and kinetics of the partial oxidation of methanol to formaldehyde on silver surfaces. Periodic density functional theory calculations employing the BEEF-vdW functional are used to identify the most stable phases of the silver surface under relevant reaction conditions and the reaction energetics are obtained on these surfaces. The calculated binding energies and transition state energies are used as input in a mean-field microkinetic model providing the reaction kinetics on silver surfaces under different reaction conditions. Our results show that, under conditions pertaining to methanol partial oxidation, oxygen is present at low concentrations and it plays a critical role in the catalytic reaction. Surface oxygen promotes the reaction by activating the OH bond in methanol, thus forming a methoxy intermediate, which can react further to form formaldehyde. Finally, the dissociation of molecular oxygen is identified as the most critical step.

Authors:
 [1];  [1];  [2];  [3];  [4]
  1. Stanford Univ., Stanford, CA (United States)
  2. Stanford Univ., Stanford, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
  3. SLAC National Accelerator Lab., Menlo Park, CA (United States)
  4. Stanford Univ., Stanford, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States); Karlsruhe Institute of Technology, Eggenstein-Leopoldshafen (Germany); Karlsruhe Institute of Technology, Karlsruhe (Germany)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1349296
Grant/Contract Number:  
AC02-76SF00515
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
ChemCatChem
Additional Journal Information:
Journal Volume: 8; Journal Issue: 23; Journal ID: ISSN 1867-3880
Publisher:
ChemPubSoc Europe
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; heterogeneous catalysis; density functional theory calculations; methanol; microkinetic model; oxidation

Citation Formats

Aljama, Hassan, Yoo, Jong Suk, Nørskov, Jens K., Abild-Pedersen, Frank, and Studt, Felix. Methanol partial oxidation on Ag(111) from first principles. United States: N. p., 2016. Web. doi:10.1002/cctc.201601053.
Aljama, Hassan, Yoo, Jong Suk, Nørskov, Jens K., Abild-Pedersen, Frank, & Studt, Felix. Methanol partial oxidation on Ag(111) from first principles. United States. doi:10.1002/cctc.201601053.
Aljama, Hassan, Yoo, Jong Suk, Nørskov, Jens K., Abild-Pedersen, Frank, and Studt, Felix. Wed . "Methanol partial oxidation on Ag(111) from first principles". United States. doi:10.1002/cctc.201601053. https://www.osti.gov/servlets/purl/1349296.
@article{osti_1349296,
title = {Methanol partial oxidation on Ag(111) from first principles},
author = {Aljama, Hassan and Yoo, Jong Suk and Nørskov, Jens K. and Abild-Pedersen, Frank and Studt, Felix},
abstractNote = {In this work, we examine the thermochemistry and kinetics of the partial oxidation of methanol to formaldehyde on silver surfaces. Periodic density functional theory calculations employing the BEEF-vdW functional are used to identify the most stable phases of the silver surface under relevant reaction conditions and the reaction energetics are obtained on these surfaces. The calculated binding energies and transition state energies are used as input in a mean-field microkinetic model providing the reaction kinetics on silver surfaces under different reaction conditions. Our results show that, under conditions pertaining to methanol partial oxidation, oxygen is present at low concentrations and it plays a critical role in the catalytic reaction. Surface oxygen promotes the reaction by activating the OH bond in methanol, thus forming a methoxy intermediate, which can react further to form formaldehyde. Finally, the dissociation of molecular oxygen is identified as the most critical step.},
doi = {10.1002/cctc.201601053},
journal = {ChemCatChem},
number = 23,
volume = 8,
place = {United States},
year = {Wed Oct 26 00:00:00 EDT 2016},
month = {Wed Oct 26 00:00:00 EDT 2016}
}

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Works referenced in this record:

A climbing image nudged elastic band method for finding saddle points and minimum energy paths
journal, December 2000

  • Henkelman, Graeme; Uberuaga, Blas P.; Jónsson, Hannes
  • The Journal of Chemical Physics, Vol. 113, Issue 22, p. 9901-9904
  • DOI: 10.1063/1.1329672