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Title: Hydroxylation of ZnO/Cu(1 1 1) inverse catalysts under ambient water vapor and the water–gas shift reaction

Abstract

The interaction of water vapor with ZnO/CuO x/Cu(1 1 1) surfaces was explored using synchrotron-based ambient pressure x-ray photoelectron spectroscopy (AP-XPS) and density-functional theory (DFT) calculations. Cu(1 1 1) does not dissociate the water molecule. Cleavage of O–H bonds was seen with AP-XPS after depositing ZnO or preparing CuO x on the copper substrate. The findings of DFT calculations show unique behavior for ZnO/CuO x/Cu(1 1 1), not seen on Cu(1 1 1), CuO x/Cu(1 1 1) or ZnO(0 0 0). The ZnO/CuO x/Cu(1 1 1) system binds water quite well and exhibits the lowest energy barrier for O–H bond cleavage. The presence of unsaturated Zn cations in the islands of ZnO led to high chemical reactivity. In order to remove the OH from ZnO/CuO x/Cu(1 1 1) and ZnO/Cu(1 1 1) surfaces, heating to elevated temperatures was necessary. At 500–600 K, a significant coverage of OH groups was still present on the surfaces and did react with CO during the water–gas shift (WGS) process. The final state of the sample depended strongly on the amount of ZnO present on the catalyst surface. For surfaces with a ZnO coverage below 0.3 ML, the adsorption of water did not change themore » integrity of the ZnO islands. On the other hand, for surfaces with a ZnO coverage above 0.3 ML, a ZnO→Zn xOH transformation was observed. This transformation led to a decrease in the WGS catalytic activity.« less

Authors:
 [1];  [1];  [2];  [3];  [4];  [3];  [1];  [5];  [5];  [2];  [3];  [6]; ORCiD logo [7]
  1. State Univ. of New York (SUNY) at Stony Brook, NY (United States). Dept. of Chemistry
  2. Universidad Central de Venezuela, Caracas (Venezuela)
  3. Brookhaven National Lab. (BNL), Upton, NY (United States). Dept. of Chemistry
  4. State Univ. of New York (SUNY) at Stony Brook, NY (United States). Dept. of Materials Science and Engineering
  5. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
  6. State Univ. of New York (SUNY) at Stony Brook, NY (United States). Dept. of Chemistry; Brookhaven National Lab. (BNL), Upton, NY (United States). Dept. of Chemistry
  7. State Univ. of New York (SUNY) at Stony Brook, NY (United States). Dept. of Chemistry; Brookhaven National Lab. (BNL), Upton, NY (United States). Dept. of Chemistry; State Univ. of New York (SUNY) at Stony Brook, NY (United States). Dept. of Materials Science and Engineering
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:
1566290
Report Number(s):
BNL-212106-2019-JAAM
Journal ID: ISSN 0022-3727
Grant/Contract Number:  
SC0012704; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physics. D, Applied Physics
Additional Journal Information:
Journal Volume: 52; Journal Issue: 45; Journal ID: ISSN 0022-3727
Publisher:
IOP Publishing
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY

Citation Formats

Orozco, Ivan, Huang, Erwei, Gutiérrez, Ramón A., Liu, Zongyuan, Zhang, Feng, Mahapatra, Mausumi, Kang, Jindong, Kersell, Heath, Nemsak, Slavomir, Ramírez, Pedro J., Senanayake, Sanjaya D., Liu, Ping, and Rodriguez, José A. Hydroxylation of ZnO/Cu(1 1 1) inverse catalysts under ambient water vapor and the water–gas shift reaction. United States: N. p., 2019. Web. doi:10.1088/1361-6463/ab37da.
Orozco, Ivan, Huang, Erwei, Gutiérrez, Ramón A., Liu, Zongyuan, Zhang, Feng, Mahapatra, Mausumi, Kang, Jindong, Kersell, Heath, Nemsak, Slavomir, Ramírez, Pedro J., Senanayake, Sanjaya D., Liu, Ping, & Rodriguez, José A. Hydroxylation of ZnO/Cu(1 1 1) inverse catalysts under ambient water vapor and the water–gas shift reaction. United States. doi:10.1088/1361-6463/ab37da.
Orozco, Ivan, Huang, Erwei, Gutiérrez, Ramón A., Liu, Zongyuan, Zhang, Feng, Mahapatra, Mausumi, Kang, Jindong, Kersell, Heath, Nemsak, Slavomir, Ramírez, Pedro J., Senanayake, Sanjaya D., Liu, Ping, and Rodriguez, José A. Wed . "Hydroxylation of ZnO/Cu(1 1 1) inverse catalysts under ambient water vapor and the water–gas shift reaction". United States. doi:10.1088/1361-6463/ab37da.
@article{osti_1566290,
title = {Hydroxylation of ZnO/Cu(1 1 1) inverse catalysts under ambient water vapor and the water–gas shift reaction},
author = {Orozco, Ivan and Huang, Erwei and Gutiérrez, Ramón A. and Liu, Zongyuan and Zhang, Feng and Mahapatra, Mausumi and Kang, Jindong and Kersell, Heath and Nemsak, Slavomir and Ramírez, Pedro J. and Senanayake, Sanjaya D. and Liu, Ping and Rodriguez, José A.},
abstractNote = {The interaction of water vapor with ZnO/CuOx/Cu(1 1 1) surfaces was explored using synchrotron-based ambient pressure x-ray photoelectron spectroscopy (AP-XPS) and density-functional theory (DFT) calculations. Cu(1 1 1) does not dissociate the water molecule. Cleavage of O–H bonds was seen with AP-XPS after depositing ZnO or preparing CuOx on the copper substrate. The findings of DFT calculations show unique behavior for ZnO/CuOx/Cu(1 1 1), not seen on Cu(1 1 1), CuOx/Cu(1 1 1) or ZnO(0 0 0). The ZnO/CuOx/Cu(1 1 1) system binds water quite well and exhibits the lowest energy barrier for O–H bond cleavage. The presence of unsaturated Zn cations in the islands of ZnO led to high chemical reactivity. In order to remove the OH from ZnO/CuOx/Cu(1 1 1) and ZnO/Cu(1 1 1) surfaces, heating to elevated temperatures was necessary. At 500–600 K, a significant coverage of OH groups was still present on the surfaces and did react with CO during the water–gas shift (WGS) process. The final state of the sample depended strongly on the amount of ZnO present on the catalyst surface. For surfaces with a ZnO coverage below 0.3 ML, the adsorption of water did not change the integrity of the ZnO islands. On the other hand, for surfaces with a ZnO coverage above 0.3 ML, a ZnO→ZnxOH transformation was observed. This transformation led to a decrease in the WGS catalytic activity.},
doi = {10.1088/1361-6463/ab37da},
journal = {Journal of Physics. D, Applied Physics},
number = 45,
volume = 52,
place = {United States},
year = {2019},
month = {8}
}

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Works referenced in this record:

Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996


Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996


Projector augmented-wave method
journal, December 1994


From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999


Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

Special points for Brillouin-zone integrations
journal, June 1976

  • Monkhorst, Hendrik J.; Pack, James D.
  • Physical Review B, Vol. 13, Issue 12, p. 5188-5192
  • DOI: 10.1103/PhysRevB.13.5188