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Title: Potassium-Promoted Reduction of Cu 2O/Cu(111) by CO

Abstract

In situ X-ray photoelectron spectroscopy (XPS), infrared reflection absorption spectroscopy (IRRAS), and scanning tunneling microscopy (STM) were used to study the reduction of potassium-modified Cu 2O/Cu(111) by CO. By following the time evolution of the O 1s peak of Cu 2O, we determined that the apparent activation energy for Cu 2O reduction by 2 × 10 –4 Torr CO is decreased by ~30% in the presence of K. On the K-modified surface, both XPS and IRRAS data show the formation of a surface species identified by IRRAS as carbonate (CO 3 2–), likely forming a K +-CO 3 2– complex, which is stable up to 500 K. STM images show that K +-CO 3 2– complexes form chains around reduced Cu islands, thereby hindering the mass transfer of Cu atoms and preventing the reconstruction of the surface. Theoretical calculations show that the formation of carbonate on the K-modified “44” Cu 2O structure is thermodynamically favorable compared to the formation of CO 2 on either the bare or K-modified surfaces.

Authors:
ORCiD logo [1];  [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Brookhaven National Lab. (BNL), Upton, NY (United States)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1559124
Report Number(s):
BNL-212024-2019-JAAM
Journal ID: ISSN 1932-7447
Grant/Contract Number:  
SC0012704
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 123; Journal Issue: 13; 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

Waluyo, Iradwikanari, Mudiyanselage, Kumudu, Xu, Fang, An, Wei, Liu, Ping, Boscoboinik, J. Anibal, Rodriguez, José A., and Stacchiola, Dario J. Potassium-Promoted Reduction of Cu2O/Cu(111) by CO. United States: N. p., 2018. Web. doi:10.1021/acs.jpcc.8b07403.
Waluyo, Iradwikanari, Mudiyanselage, Kumudu, Xu, Fang, An, Wei, Liu, Ping, Boscoboinik, J. Anibal, Rodriguez, José A., & Stacchiola, Dario J. Potassium-Promoted Reduction of Cu2O/Cu(111) by CO. United States. doi:10.1021/acs.jpcc.8b07403.
Waluyo, Iradwikanari, Mudiyanselage, Kumudu, Xu, Fang, An, Wei, Liu, Ping, Boscoboinik, J. Anibal, Rodriguez, José A., and Stacchiola, Dario J. Thu . "Potassium-Promoted Reduction of Cu2O/Cu(111) by CO". United States. doi:10.1021/acs.jpcc.8b07403. https://www.osti.gov/servlets/purl/1559124.
@article{osti_1559124,
title = {Potassium-Promoted Reduction of Cu2O/Cu(111) by CO},
author = {Waluyo, Iradwikanari and Mudiyanselage, Kumudu and Xu, Fang and An, Wei and Liu, Ping and Boscoboinik, J. Anibal and Rodriguez, José A. and Stacchiola, Dario J.},
abstractNote = {In situ X-ray photoelectron spectroscopy (XPS), infrared reflection absorption spectroscopy (IRRAS), and scanning tunneling microscopy (STM) were used to study the reduction of potassium-modified Cu2O/Cu(111) by CO. By following the time evolution of the O 1s peak of Cu2O, we determined that the apparent activation energy for Cu2O reduction by 2 × 10–4 Torr CO is decreased by ~30% in the presence of K. On the K-modified surface, both XPS and IRRAS data show the formation of a surface species identified by IRRAS as carbonate (CO32–), likely forming a K+-CO32– complex, which is stable up to 500 K. STM images show that K+-CO32– complexes form chains around reduced Cu islands, thereby hindering the mass transfer of Cu atoms and preventing the reconstruction of the surface. Theoretical calculations show that the formation of carbonate on the K-modified “44” Cu2O structure is thermodynamically favorable compared to the formation of CO2 on either the bare or K-modified surfaces.},
doi = {10.1021/acs.jpcc.8b07403},
journal = {Journal of Physical Chemistry. C},
number = 13,
volume = 123,
place = {United States},
year = {2018},
month = {11}
}

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