Oxide formation at the surface of late 4d transition metals: Insights from first-principles atomistic thermodynamics

Abstract

Using density-functional theory we assess the stability of bulk and surface oxides of the late 4d transition metals in a ``constrained equilibrium'' with a gas phase formed of O2 and CO. While the stability range of the most stable bulk oxide extends for ruthenium well into gas phase conditions representative of technological CO oxidation catalysis, this is progressively less so for the 4d metals to its right in the periodic system. Surface oxides could nevertheless still be stable under such conditions. These thermodynamic considerations are discussed in the light of recent experiments, emphasizing the role of (surface) oxides as the active phase of model catalysts formed from these metals.

7 pages including 3 figures, Related publications can be found at http://www.fhi-berlin.mpg.de/th/paper.html

References in corpus (4)

• Composition and structure of the RuO2(110) surface in an O2 and CO environment: implications for the catalytic formation of CO2
• First-principles, atomistic thermodynamics for oxidation catalysis
• The Pd(100)-(SQRT(5) x SQRT(5) R27^o)-O surface oxide revisited
• Sub-surface Oxygen and Surface Oxide Formation at Ag(111): A Density-functional Theory Investigation

Cited by in corpus (9)

• First-principles kinetic Monte Carlo simulations for heterogeneous catalysis, applied to the CO oxidation at RuO2(110)
• Alloy surface segregation in reactive environments: A first-principles atomistic thermodynamics study of Ag3Pd(111) in oxygen atmospheres
• Ab initio atomistic thermodynamics and statistical mechanics of surface properties and functions
• First-principles statistical mechanics study of the stability of a sub-nanometer thin surface oxide in reactive environments: CO oxidation at Pd(100)
• CO oxidation at Pd(100): A first-principles constrained thermodynamics study
• Density-functional theory study of the initial oxygen incorporation in Pd(111)
• CO oxidation on Pd(100) at technologically relevant pressure conditions: A first-principles kinetic Monte Carlo study
• Dissociative adsorption of methane on surface oxide structures of Pd-Pt alloys
• First-principles statistical mechanics approach to step decoration at surfaces