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Initial Reduction of the PdO(101) Surface: Role of Oxygen Vacancy Formation Kinetics

Journal Article · · Journal of Physical Chemistry. C
 [1];  [1];  [2];  [1]
  1. The Ohio State Univ., Columbus, OH (United States)
  2. Univ. of Florida, Gainesville, FL (United States)
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Here, we investigated the initial thermal reduction of the PdO(101) surface using density functional theory (DFT) calculations. The defect-free PdO(101) surface consists of parallel rows of undercoordinated Pd and O atoms (Pdcus and Ocus, respectively). DFT was used to map out the elementary processes of Ocus vacancy formation, oxygen surface atom diffusion along the Pdcus rows, and various O2 formation pathways. Because oxygen vacancies form during the reduction of the surface, the elementary processes were examined with and without the presence of adjacent Ocus vacancies. DFT calculations show that the presence of oxygen vacancies strongly affects the barriers of adjacent surface processes. Barriers for O vacancy formation are reduced by nearly 50% with an adjacent O vacancy. The barrier for O2 formation along the Pdcus row drops from 1.54 eV on the defect-free PdO(101) surface to 0.81 eV in the presence of an Ocus vacancy dimer. Yet, the presence of Ocus vacancies also leads to more strongly bound O2 on the Pdcus row. The strong neighbor effect of O vacancies on the PdO(101) surface will favor the growth of O vacancy chains and increase the rate of thermal reduction of the surface, both features that have been observed in recent ultrahigh vacuum isothermal reduction experiments of the PdO(101) surface.

Research Organization:
Univ. of Florida, Gainesville, FL (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
DOE Contract Number:
FG02-03ER15478
OSTI ID:
1593972
Journal Information:
Journal of Physical Chemistry. C, Vol. 122, Issue 45; ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English

References (68)

The universal character of the Mars and Van Krevelen mechanism November 2000
Hybrid functional studies of the oxygen vacancy in TiO 2 February 2010
Efficient hybrid density functional calculations in solids: Assessment of the Heyd–Scuseria–Ernzerhof screened Coulomb hybrid functional July 2004
Mechanism of PdO thin film formation during the oxidation of Pd(111) September 2009
“First-Principles” kinetic monte carlo simulations revisited: CO oxidation over RuO2(110) January 2012
CO Oxidation on Pt-Group Metals from Ultrahigh Vacuum to Near Atmospheric Pressures. 2. Palladium and Platinum December 2008
Atomistic lattice-gas modeling of CO oxidation on Pd(100): Temperature-programed spectroscopy and steady-state behavior April 2006
Hybrid functionals based on a screened Coulomb potential May 2003
Comparison of AP-XPS and PLIF Measurements During CO Oxidation Over Pd Single Crystals January 2016
Hybrid functional electronic structure of PbPdO 2 , a small-gap semiconductor November 2011
In Situ X-Ray Photoelectron Spectroscopy of Model Catalysts: At the Edge of the Gap March 2013
A PdO(101) thin film grown on Pd(111) in ultrahigh vacuum May 2008
Vacancy-Mediated Processes in the Oxidation of CO on PdO(101) May 2015
Methane Oxidation over PdO(101) Revealed by First-Principles Kinetic Modeling September 2015
Multi-lattice Kinetic Monte Carlo Simulations from First Principles: Reduction of the Pd(100) Surface Oxide by CO January 2015
Strong Kinetic Isotope Effect in the Dissociative Chemisorption of H 2 on a PdO(101) Thin Film May 2010
A climbing image nudged elastic band method for finding saddle points and minimum energy paths December 2000
Ab initio molecular dynamics for liquid metals December 1995
First-Principles Microkinetic Modeling of Methane Oxidation over Pd(100) and Pd(111) September 2016
Optical properties of PdO in the range of 0.5-5.4 eV April 1979
First Principles Study of Molecular O2 Adsorption on the PdO(101) Surface September 2016
In Situ Ambient Pressure XPS Study of CO Oxidation Reaction on Pd(111) Surfaces August 2012
Methane dissociation and methyl diffusion on PdO{100} January 2009
Surface structure and reactivity of Pd(100) during CO oxidation near ambient pressures January 2011
First-Principles Statistical Mechanics Study of the Stability of a Subnanometer Thin Surface Oxide in Reactive Environments: CO Oxidation at Pd(100) January 2007
Electrons to Reactors Multiscale Modeling: Catalytic CO Oxidation over RuO 2 April 2018
Pathways for C–H bond cleavage of propane σ-complexes on PdO(101) January 2012
Evidence for the Active Phase of Heterogeneous Catalysts through In Situ Reaction Product Imaging and Multiscale Modeling June 2015
Predictive Beyond-Mean-Field Rate Equations for Multisite Lattice–Gas Models of Catalytic Surface Reactions: CO Oxidation on Pd(100) December 2016
CO Oxidation on Pd(111): A First-Principles-Based Kinetic Monte Carlo Study May 2014
Comment on “CO Oxidation on Pt-Group Metals from Ultrahigh Vacuum to Near Atmospheric Pressures. 2. Palladium and Platinum” March 2010
In Situ Optical Reflectance Difference Observations of CO Oxidation over Pd(100) May 2017
Improved electronic structure and magnetic exchange interactions in transition metal oxides October 2017
Effects of non-local exchange on core level shifts for gas-phase and adsorbed molecules July 2014
Understanding the Intrinsic Surface Reactivity of Single-Layer and Multilayer PdO(101) on Pd(100) August 2018
Surface structural evolution during the thermal decomposition of a PdO(101) thin film October 2011
High Selectivity for Primary C–H Bond Cleavage of Propane σ-Complexes on the PdO(101) Surface October 2011
Surface science under reaction conditions: CO oxidation on Pt and Pd model catalysts January 2017
Adsorption of CO 2 on a PdO(101) Thin Film January 2012
Surface Chemistry of Late Transition Metal Oxides December 2012
CO Oxidation on PdO(101) during Temperature-Programmed Reaction Spectroscopy: Role of Oxygen Vacancies November 2014
Travelling fronts of the CO oxidation on Pd(111) with coverage-dependent diffusion October 2014
First-principles kinetic Monte Carlo simulations for heterogeneous catalysis: Application to the CO oxidation at Ru O 2 ( 110 ) January 2006
CO Oxidation on the Pd(111) Surface September 2014
CO oxidation trends on Pt-group metals from ultrahigh vacuum to near atmospheric pressures: A combined in situ PM-IRAS and reaction kinetics study January 2009
Disentangling the role of small polarons and oxygen vacancies in Ce O 2 June 2017
Electronic structure and oxygen vacancies in PdO and ZnO: validation of DFT models January 2011
The semiconductivity and stability of palladium oxide April 1978
Visualization of Gas Distribution in a Model AP-XPS Reactor by PLIF: CO Oxidation over a Pd(100) Catalyst January 2017
Alkane activation on crystalline metal oxide surfaces January 2014
Electronic structure of noble-metal monoxides: PdO, PtO, and AgO February 1994
Active Surfaces for CO Oxidation on Palladium in the Hyperactive State December 2010
Kinetic Coupling among Metal and Oxide Phases during CO Oxidation on Partially Reduced PdO(101): Influence of Gas-Phase Composition September 2017
The electronic structure of PdO found by photoemission (UPS and XPS) and inverse photoemission (BIS) May 1997
Highly active surfaces for CO oxidation on Rh, Pd, and Pt December 2007
CO oxidation on single and multilayer Pd oxides on Pd(111): mechanistic insights from RAIRS January 2014
Examination of Oxygen Vacancy Formation in Mn-Doped CeO 2 (111) Using DFT+U and the Hybrid Functional HSE06 July 2013
Choice of U for DFT+ U Calculations for Titanium Oxides March 2011
Dynamics and Thermodynamics of Pd–PdO Phase Transitions: Effects of Pd Cluster Size and Kinetic Implications for Catalytic Methane Combustion January 2016
Steady-State CO Oxidation on Pd(111): First-Principles Kinetic Monte Carlo Simulations and Microkinetic Analysis October 2016
Formation of Thin Films of PdO and Their Electric Properties June 1967
Molecular Chemisorption of O 2 on a PdO(101) Thin Film on Pd(111) May 2008
The Role of Oxides in Catalytic CO Oxidation over Rhodium and Palladium April 2018
Screened Hybrid Exact Exchange Correction Scheme for Adsorption Energies on Perovskite Oxides July 2015
New insights into catalytic CO oxidation on Pt-group metals at elevated pressures February 2009
Dispersion-corrected density functional theory calculations of the molecular binding of n -alkanes on Pd(111) and PdO(101) February 2012
Simultaneous Imaging of Gas Phase over and Surface Reflectance of a Pd(100) Single Crystal during CO Oxidation October 2017
Dissociative Adsorption of Water on an H 2 O/GaAs(100) Interface: In Situ Near-Ambient Pressure XPS Studies February 2014

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