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

Journal Article · · Journal of Physics. D, Applied Physics
 [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
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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.

Research Organization:
Brookhaven National Laboratory (BNL), Upton, NY (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
AC02-05CH11231; SC0012704
OSTI ID:
1566290
Report Number(s):
BNL--212106-2019-JAAM
Journal Information:
Journal of Physics. D, Applied Physics, Journal Name: Journal of Physics. D, Applied Physics Journal Issue: 45 Vol. 52; ISSN 0022-3727
Publisher:
IOP PublishingCopyright Statement
Country of Publication:
United States
Language:
English

References (46)

Metal Oxide Catalysis book October 2008
Formation of a ZnO Overlayer in Industrial Cu/ZnO/Al 2 O 3 Catalysts Induced by Strong Metal-Support Interactions journal February 2015
Chemical Activity of Thin Oxide Layers: Strong Interactions with the Support Yield a New Thin-Film Phase of ZnO journal September 2013
Formation of a ZnO Overlayer in Industrial Cu/ZnO/Al 2 O 3 Catalysts Induced by Strong Metal-Support Interactions journal February 2015
Mechanistic Study of CO Titration on Cu x O/Cu(1 1 1) ( x ≤2) Surfaces journal June 2014
Potassium-Induced Effect on the Structure and Chemical Activity of the Cu x O/Cu(1 1 1) ( x ≤ 2) Surface: A Combined Scanning Tunneling Microscopy and Density Functional Theory Study journal November 2015
Nanostructured Oxides in Chemistry: Characterization and Properties journal November 2004
Methanol Synthesis journal September 2012
IR-Spectroscopic Study on the Interface of Cu-Based Methanol Synthesis Catalysts: Evidence for the Formation of a ZnO Overlayer journal August 2017
H2O adsorption on Cu2O(100) journal October 1991
Vanadium oxide monolayer catalysts Preparation, characterization and catalytic activity journal April 1991
Auger and direct electron spectra in X-ray photoelectron studies of zinc, zinc oxide, gallium and gallium oxide journal January 1973
Methanol Synthesis journal May 1992
Methanol synthesis journal December 1995
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set journal July 1996
Methanol Synthesis book January 1982
The behavior of inverse oxide/metal catalysts: CO oxidation and water-gas shift reactions over ZnO/Cu(111) surfaces journal March 2019
ZnO(101̅0) Surface Hydroxylation under Ambient Water Vapor journal August 2017
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
Enhancing Dissociative Adsorption of Water on Cu(111) via Chemisorbed Oxygen journal May 2017
Water Adsorption on Cu 2 O(111) Surfaces: A Scanning Tunneling Microscopy Study journal September 2017
Growth, Structure, and Catalytic Properties of ZnO x Grown on CuO x /Cu(111) Surfaces journal October 2018
Potassium and Water Coadsorption on TiO 2 (110): OH-Induced Anchoring of Potassium and the Generation of Single-Site Catalysts journal September 2016
Nanostructured Oxides in Chemistry:  Characterization and Properties journal September 2004
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
Catalysis Science of Bulk Mixed Oxides journal April 2012
On the Mechanism of Low-Temperature Water Gas Shift Reaction on Copper journal January 2008
Hydrogen-Bonded Cyclic Water Clusters Nucleated on an Oxide Surface journal September 2014
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
Water Adsorption on ZnO(0001): Transition from Triangular Surface Structures to a Disordered Hydroxyl Terminated phase journal June 2010
Adsorption of Water on Cu 2 O and Al 2 O 3 Thin Films journal June 2008
Water Dissociation and KOH Formation on Potassium-Covered MgO/Ru(001) journal December 1998
Reducing Dzyaloshinskii-Moriya interaction and field-free spin-orbit torque switching in synthetic antiferromagnets journal May 2021
High-resolution X-ray luminescence extension imaging journal February 2021
Electronic structure of AlFeN films exhibiting crystallographic orientation change from c- to a-axis with Fe concentrations and annealing effect journal February 2020
Improved tangent estimate in the nudged elastic band method for finding minimum energy paths and saddle points journal December 2000
Water-gas-shift reaction on metal nanoparticles and surfaces journal April 2007
Effect of the exchange-correlation potential and of surface relaxation on the description of the H2O dissociation on Cu(111) journal June 2009
Water-gas shift reaction on oxide/Cu(111): Rational catalyst screening from density functional theory journal November 2010
Water Gas Shift Catalysis journal September 2009
Special points for Brillouin-zone integrations journal June 1976
Projector augmented-wave method journal December 1994
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
Generalized Gradient Approximation Made Simple journal October 1996
Active sites for CO 2 hydrogenation to methanol on Cu/ZnO catalysts journal March 2017

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