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Title: Oxygen-Promoted Methane Activation on Copper

Abstract

The role of oxygen in the activation of C–H bonds in methane on clean and oxygen-precovered Cu(111) and Cu 2O(111) surfaces was studied with combined in situ near-ambient-pressure scanning tunneling microscopy and X-ray photoelectron spectroscopy. Activation of methane at 300 K and “moderate pressures” was only observed on oxygen-precovered Cu(111) surfaces. Density functional theory calculations reveal that the lowest activation energy barrier of C–H on Cu(111) in the presence of chemisorbed oxygen is related to a two-active-site, four-centered mechanism, which stabilizes the required transition-state intermediate by dipole–dipole attraction of O–H and Cu–CH 3 species. Furthermore, the C–H bond activation barriers on Cu 2O(111) surfaces are large due to the weak stabilization of H and CH 3 fragments.

Authors:
 [1];  [2];  [3]; ORCiD logo [3];  [4];  [5]; ORCiD logo [5]; ORCiD logo [5]
  1. Brookhaven National Lab. (BNL), Upton, NY (United States); Nanjing Univ. of Science & Technology, Xiaolingwei (China)
  2. Xi'an Jiaotong Univ., Xi'an (China)
  3. State Univ. of New York, Binghamton, NY (United States)
  4. Harvard Univ., Cambridge, MA (United States)
  5. Brookhaven National Lab. (BNL), Upton, NY (United States)
Publication Date:
Research Org.:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1411144
Report Number(s):
BNL-114713-2017-JA
Journal ID: ISSN 1520-6106; KC0403020; TRN: US1800182
Grant/Contract Number:
SC0012704
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry
Additional Journal Information:
Journal Volume: 122; Journal Issue: 2; Journal ID: ISSN 1520-6106
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
77 NANOSCIENCE AND NANOTECHNOLOGY

Citation Formats

Niu, Tianchao, Jiang, Zhao, Zhu, Yaguang, Zhou, Guangwen, van Spronsen, Matthijs A., Tenney, Samuel A., Boscoboinik, J. Anibal, and Stacchiola, Dario. Oxygen-Promoted Methane Activation on Copper. United States: N. p., 2017. Web. doi:10.1021/acs.jpcb.7b06956.
Niu, Tianchao, Jiang, Zhao, Zhu, Yaguang, Zhou, Guangwen, van Spronsen, Matthijs A., Tenney, Samuel A., Boscoboinik, J. Anibal, & Stacchiola, Dario. Oxygen-Promoted Methane Activation on Copper. United States. doi:10.1021/acs.jpcb.7b06956.
Niu, Tianchao, Jiang, Zhao, Zhu, Yaguang, Zhou, Guangwen, van Spronsen, Matthijs A., Tenney, Samuel A., Boscoboinik, J. Anibal, and Stacchiola, Dario. Wed . "Oxygen-Promoted Methane Activation on Copper". United States. doi:10.1021/acs.jpcb.7b06956.
@article{osti_1411144,
title = {Oxygen-Promoted Methane Activation on Copper},
author = {Niu, Tianchao and Jiang, Zhao and Zhu, Yaguang and Zhou, Guangwen and van Spronsen, Matthijs A. and Tenney, Samuel A. and Boscoboinik, J. Anibal and Stacchiola, Dario},
abstractNote = {The role of oxygen in the activation of C–H bonds in methane on clean and oxygen-precovered Cu(111) and Cu2O(111) surfaces was studied with combined in situ near-ambient-pressure scanning tunneling microscopy and X-ray photoelectron spectroscopy. Activation of methane at 300 K and “moderate pressures” was only observed on oxygen-precovered Cu(111) surfaces. Density functional theory calculations reveal that the lowest activation energy barrier of C–H on Cu(111) in the presence of chemisorbed oxygen is related to a two-active-site, four-centered mechanism, which stabilizes the required transition-state intermediate by dipole–dipole attraction of O–H and Cu–CH3 species. Furthermore, the C–H bond activation barriers on Cu2O(111) surfaces are large due to the weak stabilization of H and CH3 fragments.},
doi = {10.1021/acs.jpcb.7b06956},
journal = {Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry},
number = 2,
volume = 122,
place = {United States},
year = {Wed Nov 01 00:00:00 EDT 2017},
month = {Wed Nov 01 00:00:00 EDT 2017}
}

Journal Article:
Free Publicly Available Full Text
This content will become publicly available on November 1, 2018
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