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 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.
- Authors:
-
[3];
[5];
[5]
- Brookhaven National Lab. (BNL), Upton, NY (United States); Nanjing Univ. of Science & Technology, Xiaolingwei (China)
- Xi'an Jiaotong Univ., Xi'an (China)
- State Univ. of New York, Binghamton, NY (United States)
- Harvard Univ., Cambridge, MA (United States)
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- Publication Date:
- Research Org.:
- Brookhaven National Lab. (BNL), Upton, NY (United States); Energy Frontier Research Centers (EFRC) (United States). Integrated Mesoscale Architectures for Sustainable Catalysis (IMASC)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1411144
- Report Number(s):
- BNL-114713-2017-JA
Journal ID: ISSN 1520-6106; KC0403020; TRN: US1800182
- Grant/Contract Number:
- SC0012704
- Resource Type:
- 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. https://doi.org/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. https://doi.org/10.1021/acs.jpcb.7b06956. https://www.osti.gov/servlets/purl/1411144.
@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}
}
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