skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

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

Abstract

© 2019 IOP Publishing Ltd. The interaction of water vapor with ZnO/CuOx/Cu(1 1 1) surfaces was investigated 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 results 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 integritymore » 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.« 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); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1566290
Alternate Identifier(s):
OSTI ID: 1656528
Report Number(s):
BNL-212106-2019-JAAM
Journal ID: ISSN 0022-3727; TRN: US2000984
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. https://www.osti.gov/servlets/purl/1566290.
@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 = {© 2019 IOP Publishing Ltd. The interaction of water vapor with ZnO/CuOx/Cu(1 1 1) surfaces was investigated 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 results 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}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 2 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

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

Water Dissociation and KOH Formation on Potassium-Covered MgO/Ru(001)
journal, December 1998

  • Huang, H. H.; Jiang, X.; Siew, H. L.
  • Langmuir, Vol. 14, Issue 25
  • DOI: 10.1021/la980616q

Water Adsorption on Cu 2 O(111) Surfaces: A Scanning Tunneling Microscopy Study
journal, September 2017

  • Möller, Christoph; Nilius, Niklas
  • The Journal of Physical Chemistry C, Vol. 121, Issue 38
  • DOI: 10.1021/acs.jpcc.7b06996

Potassium and Water Coadsorption on TiO 2 (110): OH-Induced Anchoring of Potassium and the Generation of Single-Site Catalysts
journal, September 2016

  • Grinter, David C.; R. Remesal, Elena; Luo, Si
  • The Journal of Physical Chemistry Letters, Vol. 7, Issue 19
  • DOI: 10.1021/acs.jpclett.6b01623

Formation of a ZnO Overlayer in Industrial Cu/ZnO/Al 2 O 3 Catalysts Induced by Strong Metal-Support Interactions
journal, February 2015

  • Lunkenbein, Thomas; Schumann, Julia; Behrens, Malte
  • Angewandte Chemie International Edition, Vol. 54, Issue 15
  • DOI: 10.1002/anie.201411581

On the Mechanism of Low-Temperature Water Gas Shift Reaction on Copper
journal, January 2008

  • Gokhale, Amit A.; Dumesic, James A.; Mavrikakis, Manos
  • Journal of the American Chemical Society, Vol. 130, Issue 4
  • DOI: 10.1021/ja0768237

Low-Temperature Conversion of Methane to Methanol on CeO x /Cu 2 O Catalysts: Water Controlled Activation of the C–H Bond
journal, October 2016

  • Zuo, Zhijun; Ramírez, Pedro J.; Senanayake, Sanjaya D.
  • Journal of the American Chemical Society, Vol. 138, Issue 42
  • DOI: 10.1021/jacs.6b08668

Projector augmented-wave method
journal, December 1994


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


Water-gas shift reaction on oxide/Cu(111): Rational catalyst screening from density functional theory
journal, November 2010

  • Liu, Ping
  • The Journal of Chemical Physics, Vol. 133, Issue 20
  • DOI: 10.1063/1.3506897

Hydrogen-Bonded Cyclic Water Clusters Nucleated on an Oxide Surface
journal, September 2014

  • Kronawitter, Coleman X.; Riplinger, Christoph; He, Xiaobo
  • Journal of the American Chemical Society, Vol. 136, Issue 38
  • DOI: 10.1021/ja5056214

Nanostructured Oxides in Chemistry:  Characterization and Properties
journal, September 2004

  • Fernández-García, M.; Martínez-Arias, A.; Hanson, J. C.
  • Chemical Reviews, Vol. 104, Issue 9
  • DOI: 10.1021/cr030032f

Water-gas-shift reaction on metal nanoparticles and surfaces
journal, April 2007

  • Liu, Ping; Rodriguez, José A.
  • The Journal of Chemical Physics, Vol. 126, Issue 16
  • DOI: 10.1063/1.2722747

Effect of the exchange-correlation potential and of surface relaxation on the description of the H2O dissociation on Cu(111)
journal, June 2009

  • Fajín, José L. C.; Illas, Francesc; Gomes, José R. B.
  • The Journal of Chemical Physics, Vol. 130, Issue 22
  • DOI: 10.1063/1.3149851

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

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


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


H2O adsorption on Cu2O(100)
journal, October 1991


Vanadium oxide monolayer catalysts Preparation, characterization and catalytic activity
journal, April 1991


Chemical Activity of Thin Oxide Layers: Strong Interactions with the Support Yield a New Thin-Film Phase of ZnO
journal, September 2013

  • Schott, Vadim; Oberhofer, Harald; Birkner, Alexander
  • Angewandte Chemie International Edition, Vol. 52, Issue 45
  • DOI: 10.1002/anie.201302315

IR-Spectroscopic Study on the Interface of Cu-Based Methanol Synthesis Catalysts: Evidence for the Formation of a ZnO Overlayer
journal, August 2017


Mechanistic Study of CO Titration on Cu x O/Cu(1 1 1) ( x ≤2) Surfaces
journal, June 2014


Enhancing Dissociative Adsorption of Water on Cu(111) via Chemisorbed Oxygen
journal, May 2017

  • Liu, Qianqian; Li, Jonathan; Tong, Xiao
  • The Journal of Physical Chemistry C, Vol. 121, Issue 22
  • DOI: 10.1021/acs.jpcc.6b12897

Active sites for CO 2 hydrogenation to methanol on Cu/ZnO catalysts
journal, March 2017


The behavior of inverse oxide/metal catalysts: CO oxidation and water-gas shift reactions over ZnO/Cu(111) surfaces
journal, March 2019


Adsorption of Water on Cu 2 O and Al 2 O 3 Thin Films
journal, June 2008

  • Deng, Xingyi; Herranz, Tirma; Weis, Christoph
  • The Journal of Physical Chemistry C, Vol. 112, Issue 26
  • DOI: 10.1021/jp800944r

Water Adsorption on ZnO(0001): Transition from Triangular Surface Structures to a Disordered Hydroxyl Terminated phase
journal, June 2010

  • Önsten, Anneli; Stoltz, Dunja; Palmgren, Pål
  • The Journal of Physical Chemistry C, Vol. 114, Issue 25
  • DOI: 10.1021/jp1004677

Catalysis Science of Bulk Mixed Oxides
journal, April 2012

  • Wachs, Israel E.; Routray, Kamalakanta
  • ACS Catalysis, Vol. 2, Issue 6
  • DOI: 10.1021/cs2005482

Auger and direct electron spectra in X-ray photoelectron studies of zinc, zinc oxide, gallium and gallium oxide
journal, January 1973


Improved tangent estimate in the nudged elastic band method for finding minimum energy paths and saddle points
journal, December 2000

  • Henkelman, Graeme; Jónsson, Hannes
  • The Journal of Chemical Physics, Vol. 113, Issue 22
  • DOI: 10.1063/1.1323224

Fundamental Studies of Well-Defined Surfaces of Mixed-Metal Oxides: Special Properties of MO x /TiO 2 (110) {M = V, Ru, Ce, or W}
journal, December 2012

  • Stacchiola, Darío J.; Senanayake, Sanjaya D.; Liu, Ping
  • Chemical Reviews, Vol. 113, Issue 6
  • DOI: 10.1021/cr300316v

Hydrogenation of CO 2 on ZnO/Cu(100) and ZnO/Cu(111) Catalysts: Role of Copper Structure and Metal–Oxide Interface in Methanol Synthesis
journal, August 2017

  • Palomino, Robert M.; Ramírez, Pedro J.; Liu, Zongyuan
  • The Journal of Physical Chemistry B, Vol. 122, Issue 2
  • DOI: 10.1021/acs.jpcb.7b06901

ZnO(101̅0) Surface Hydroxylation under Ambient Water Vapor
journal, August 2017

  • Newberg, John T.; Goodwin, Chris; Arble, Chris
  • The Journal of Physical Chemistry B, Vol. 122, Issue 2
  • DOI: 10.1021/acs.jpcb.7b03335

Water Gas Shift Catalysis
journal, September 2009


Growth, Structure, and Catalytic Properties of ZnO x Grown on CuO x /Cu(111) Surfaces
journal, October 2018

  • Mahapatra, Mausumi; Kang, Jindong; Ramírez, Pedro J.
  • The Journal of Physical Chemistry C, Vol. 122, Issue 46
  • DOI: 10.1021/acs.jpcc.8b09243

Formation of a ZnO Overlayer in Industrial Cu/ZnO/Al 2 O 3 Catalysts Induced by Strong Metal-Support Interactions
journal, February 2015

  • Lunkenbein, Thomas; Schumann, Julia; Behrens, Malte
  • Angewandte Chemie, Vol. 127, Issue 15
  • DOI: 10.1002/ange.201411581

Methanol Synthesis
journal, September 2012