CO oxidation at Pd(100): A first-principles constrained thermodynamics study

Abstract

The possible formation of oxides or thin oxide films (surface oxides) on late transition metal surfaces is recently being recognized as an essential ingredient when aiming to understand catalytic oxidation reactions under technologically relevant gas phase conditions. Using the CO oxidation at Pd(100) as example, we investigate the composition and structure of this model catalyst surface over a wide range of (T,p)-conditions within a multiscale modeling approach where density-functional theory is linked to thermodynamics. The results show that under the catalytically most relevant gas phase conditions a thin surface oxide is the most stable "phase" and that the system is actually very close to a transition between this oxidic state and a reduced state in form of a CO covered Pd(100) surface.

13 pages including 7 figures; related publications can be found at http://www.fhi-berlin.mpg.de/th/th.html

References in corpus (10)

• Composition, structure and stability of RuO_2(110) as a function of oxygen pressure
• The hematite (alpha-Fe_2 O_3) (0001) surface: evidence for domains of distinct chemistry
• Composition and structure of the RuO2(110) surface in an O2 and CO environment: implications for the catalytic formation of CO2
• The Effect of the Environment on alpha-Al_2O_3 (0001) Surface Structures
• First-principles, atomistic thermodynamics for oxidation catalysis
• Kinetic hindrance during the initial oxidation of Pd(100) at ambient pressures
• The Pd(100)-(SQRT(5) x SQRT(5) R27^o)-O surface oxide revisited
• Why is a noble metal catalytically active? The role of the O-Ag interaction in the function of silver as an oxidation catalyst
• Oxide formation at the surface of late 4d transition metals: Insights from first-principles atomistic thermodynamics
• Comparison of the full-potential and frozen-core approximation approaches to density-functional calculations of surfaces

Cited by in corpus (5)

• Using atomic layer deposition to hinder solvent decomposition in lithium ion batteries: first principles modeling and experimental studies
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• Ab initio thermodynamic study of SnO${}_2$(110) surface in an O${}_2$ and NO environment: a fundamental understanding of gas sensing mechanism for NO and NO${}_2$
• CO oxidation on Pd(100) vs. PdO(sqrt5xsqrt5)R27^o: First-Principles Kinetic Phase Diagrams and Bistability Conditions
• First-principles statistical mechanics approach to step decoration at surfaces