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Title: Oxidation of palladium on Au(111) and ZnO(0001) supports

Abstract

The oxidation of supported Pd-deposits on Au(111) and ZnO(0001) single crystals has been studied by x- ray photoemission spectroscopy (XPS). Oxidation has been carried out ex-situ in a high-pressure cell with subsequent vacuum-transfer and characterization by XPS in ultrahigh vacuum (UHV), as well as using in-situ characterization by synchrotron based near-ambient pressure XPS. On Au(111) alloying of Pd with the substrate competes with oxidation and only sufficiently thick Pd films have been found to oxidize. For Pd on ZnO the oxidation conditions depend on the amount of deposited Pd. Thicker Pd deposits behave similar to bulk Pd, while thinner films oxidize already at lower temperatures. Interestingly, for very small amounts of Pd, in-situ XPS shows full oxidation at room temperature and at less than 0.6 mbar O₂ pressure. This indicates a lowering of the kinetic barriers for oxidation of very small supported Pd-clusters. The formed oxide is, however, not stable in UHV and a slow reduction is observed. The instability of this oxide indicates that the Pd-oxide formed at the interface to ZnO may have different chemical properties compared to bulk PdO or surface oxides on Pd.

Authors:
 [1];  [2];  [1];  [2];  [1]
  1. Univ. of South Florida, Tampa, FL (United States). Dept. of Physics
  2. Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials
Publication Date:
Research Org.:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1182507
Alternate Identifier(s):
OSTI ID: 1224232
Report Number(s):
BNL-107469-2015-JA
Journal ID: ISSN 0021-9606; JCPSA6; R&D Project: 16080/16080; KC0403020; TRN: US1500506
Grant/Contract Number:  
SC00112704; AC02-98CH10886; FG02-09ER1608
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 141; Journal Issue: 15; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; X-ray photoelectron spectroscopy; oxide surfaces; surface oxidation; gold; x-ray photoemission spectroscopy; palladium catalysts

Citation Formats

Lallo, J., Tenney, S. A., Kramer, A., Sutter, P., and Batzill, M. Oxidation of palladium on Au(111) and ZnO(0001) supports. United States: N. p., 2014. Web. doi:10.1063/1.4898086.
Lallo, J., Tenney, S. A., Kramer, A., Sutter, P., & Batzill, M. Oxidation of palladium on Au(111) and ZnO(0001) supports. United States. https://doi.org/10.1063/1.4898086
Lallo, J., Tenney, S. A., Kramer, A., Sutter, P., and Batzill, M. Tue . "Oxidation of palladium on Au(111) and ZnO(0001) supports". United States. https://doi.org/10.1063/1.4898086. https://www.osti.gov/servlets/purl/1182507.
@article{osti_1182507,
title = {Oxidation of palladium on Au(111) and ZnO(0001) supports},
author = {Lallo, J. and Tenney, S. A. and Kramer, A. and Sutter, P. and Batzill, M.},
abstractNote = {The oxidation of supported Pd-deposits on Au(111) and ZnO(0001) single crystals has been studied by x- ray photoemission spectroscopy (XPS). Oxidation has been carried out ex-situ in a high-pressure cell with subsequent vacuum-transfer and characterization by XPS in ultrahigh vacuum (UHV), as well as using in-situ characterization by synchrotron based near-ambient pressure XPS. On Au(111) alloying of Pd with the substrate competes with oxidation and only sufficiently thick Pd films have been found to oxidize. For Pd on ZnO the oxidation conditions depend on the amount of deposited Pd. Thicker Pd deposits behave similar to bulk Pd, while thinner films oxidize already at lower temperatures. Interestingly, for very small amounts of Pd, in-situ XPS shows full oxidation at room temperature and at less than 0.6 mbar O₂ pressure. This indicates a lowering of the kinetic barriers for oxidation of very small supported Pd-clusters. The formed oxide is, however, not stable in UHV and a slow reduction is observed. The instability of this oxide indicates that the Pd-oxide formed at the interface to ZnO may have different chemical properties compared to bulk PdO or surface oxides on Pd.},
doi = {10.1063/1.4898086},
journal = {Journal of Chemical Physics},
number = 15,
volume = 141,
place = {United States},
year = {Tue Oct 21 00:00:00 EDT 2014},
month = {Tue Oct 21 00:00:00 EDT 2014}
}

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Works referenced in this record:

Factors Affecting the Catalytic Activity of Pd/ZrO2for the Combustion of Methane
journal, May 1998

  • Carstens, Jason N.; Su, Stephen C.; Bell, Alexis T.
  • Journal of Catalysis, Vol. 176, Issue 1
  • DOI: 10.1006/jcat.1998.2029

Oscillatory CO oxidation on Pd(100) studied with in situ scanning tunneling microscopy
journal, March 2004


Oscillatory oxidation of CO over Pt, Pd and Ir catalysts: Theory
journal, February 1982


Transformation of methanol in the presence of steam and oxygen over ZnO-supported transition metal catalysts under stream reforming conditions
journal, September 2005


Recent advances in direct formic acid fuel cells (DFAFC)
journal, July 2008


High Selectivity for Primary C–H Bond Cleavage of Propane σ-Complexes on the PdO(101) Surface
journal, October 2011

  • Weaver, Jason F.; Hakanoglu, Can; Antony, Abbin
  • Journal of the American Chemical Society, Vol. 133, Issue 40
  • DOI: 10.1021/ja206599k

In situ XPS study of Pd(111) oxidation at elevated pressure, Part 2: Palladium oxidation in the 10−1mbar range
journal, August 2006


Interaction of O2 with Pd single crystals in the range 1–150Torr: Oxygen dissolution and reaction
journal, July 2006


A PdO(101) thin film grown on Pd(111) in ultrahigh vacuum
journal, May 2008


Mechanism of PdO thin film formation during the oxidation of Pd(111)
journal, September 2009


In Situ Spectroscopic Study of the Oxidation and Reduction of Pd(111)
journal, December 2005

  • Ketteler, Guido; Ogletree, D. Frank; Bluhm, Hendrik
  • Journal of the American Chemical Society, Vol. 127, Issue 51
  • DOI: 10.1021/ja055754y

The Pd()–R27°-O surface oxide revisited
journal, September 2003


Photoemission spectra and thermal desorption characteristics of two states of oxygen on Pd
journal, February 1980


Interaction of oxygen with Pd(111): High effective O2 pressure conditions by using nitrogen dioxide
journal, June 1990


Interaction of NO and O2 with Pd(111) surfaces. I.
journal, June 1977


The oxidation of Pd(111)
journal, August 2000


XPS analysis of palladium oxide layers and particles
journal, April 1996


XPS analysis of the oxidation of palladium model catalysts
journal, January 1999


Kinetic Hindrance during the Initial Oxidation of Pd(100) at Ambient Pressures
journal, January 2004


Oxidation and reduction of Pd(100) and aerosol-deposited Pd nanoparticles
journal, March 2011


In situ XPS study of Pd(111) oxidation. Part 1: 2D oxide formation in 10−3mbar O2
journal, March 2006


Kinetics of Palladium Oxidation in the mbar Pressure Range: Ambient Pressure XPS Study
journal, May 2013

  • Zemlyanov, Dmitry; Klötzer, Bernhard; Gabasch, Harald
  • Topics in Catalysis, Vol. 56, Issue 11
  • DOI: 10.1007/s11244-013-0052-z

Lack of surface oxide layers and facile bulk oxide formation on Pd(110)
journal, September 2009


Stressing Pd atoms: Initial oxidation of the Pd(110) surface
journal, July 2008


Development of a ReaxFF potential for Pd/O and application to palladium oxide formation
journal, July 2013

  • Senftle, Thomas P.; Meyer, Randall J.; Janik, Michael J.
  • The Journal of Chemical Physics, Vol. 139, Issue 4
  • DOI: 10.1063/1.4815820

Combinatorial high-energy x-ray microbeam study of the size-dependent oxidation of Pd nanoparticles on MgO(100)
journal, March 2008


Size-Dependent Oxidation Mechanism of Supported Pd Nanoparticles
journal, May 2006

  • Schalow, Tobias; Brandt, Björn; Starr, David E.
  • Angewandte Chemie International Edition, Vol. 45, Issue 22
  • DOI: 10.1002/anie.200504253

Oxygen Storage at the Metal/Oxide Interface of Catalyst Nanoparticles
journal, November 2005

  • Schalow, Tobias; Laurin, Mathias; Brandt, Björn
  • Angewandte Chemie International Edition, Vol. 44, Issue 46
  • DOI: 10.1002/anie.200502160

Formation of interface and surface oxides on supported Pd nanoparticles
journal, June 2006


Angle‐resolved x‐ray photoelectron spectroscopy method for the thickness measurement of metal oxide/metal ultrathin films
journal, July 1993

  • Chen, Liangyu; Hoffman, Richard W.
  • Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films, Vol. 11, Issue 4
  • DOI: 10.1116/1.578366

Reaction of CH 3 OH on Pd/ZnO(0001) and PdZn/ZnO(0001) Model Catalysts
journal, May 2007

  • Bera, Parthasarathi; Vohs, John M.
  • The Journal of Physical Chemistry C, Vol. 111, Issue 19
  • DOI: 10.1021/jp068501f

Oxygen-induced Restructuring of a Pd/Fe3O4 Model Catalyst
journal, March 2006


Oxygen adsorption on Cu Zn O ( 0001 ) Zn
journal, January 2008


Growth and structure of Pd films on ZnO(0001)
journal, October 2006

  • Bera, Parthasarathi; Vohs, John M.
  • The Journal of Chemical Physics, Vol. 125, Issue 16
  • DOI: 10.1063/1.2363186

Pd–Au bimetallic catalysts: understanding alloy effects from planar models and (supported) nanoparticles
journal, January 2012

  • Gao, Feng; Goodman, D. Wayne
  • Chemical Society Reviews, Vol. 41, Issue 24
  • DOI: 10.1039/c2cs35160a

The Composition and Structure of Pd−Au Surfaces
journal, October 2005

  • Yi, C. -W.; Luo, K.; Wei, T.
  • The Journal of Physical Chemistry B, Vol. 109, Issue 39
  • DOI: 10.1021/jp053515r

In Situ X-Ray Photoelectron Spectroscopy of Model Catalysts: At the Edge of the Gap
journal, March 2013


Works referencing / citing this record:

MEMS-Based Gas Sensor Using PdO-Decorated TiO2 Thin Film for Highly Sensitive and Selective H2 Detection with Low Power Consumption
journal, March 2018

  • Kwak, Seungmin; Shim, Young-Seok; Yoo, Yong Kyoung
  • Electronic Materials Letters, Vol. 14, Issue 3
  • DOI: 10.1007/s13391-018-0030-5

Sputtered PdO Decorated TiO 2 Sensing Layer for a Hydrogen Gas Sensor
journal, January 2018

  • Lee, Jeong Hoon; Kwak, Seungmin; Lee, Jin-Hyung
  • Journal of Nanomaterials, Vol. 2018
  • DOI: 10.1155/2018/8678519