Kinetics of the sulfur oxidation on palladium: A combined in situ x-ray photoelectron spectroscopy and density-functional study

  • We studied the reaction kinetics of sulfur oxidation on the Pd(100) surface by in situ high resolution x-ray photoelectron spectroscopy and ab initio density functional calculations. Isothermal oxidation experiments were performed between 400 and 500 K for small amounts (∼0.02 ML) of preadsorbed sulfur, with oxygen in large excess. The main stable reaction intermediate found on the surface is SO4, with SO2 and SO3 being only present in minor amounts. Density-functional calculations depict a reaction energy profile, which explains the sequential formation of SO2, SO3, and eventually SO4, also highlighting that the in-plane formation of SO from S and O adatoms is the rate limiting step. From tWe studied the reaction kinetics of sulfur oxidation on the Pd(100) surface by in situ high resolution x-ray photoelectron spectroscopy and ab initio density functional calculations. Isothermal oxidation experiments were performed between 400 and 500 K for small amounts (∼0.02 ML) of preadsorbed sulfur, with oxygen in large excess. The main stable reaction intermediate found on the surface is SO4, with SO2 and SO3 being only present in minor amounts. Density-functional calculations depict a reaction energy profile, which explains the sequential formation of SO2, SO3, and eventually SO4, also highlighting that the in-plane formation of SO from S and O adatoms is the rate limiting step. From the experiments we determined the activation energy of the rate limiting step to be 85 ± 6 kJ mol−1 by Arrhenius analysis, matching the calculated endothermicity of the SO formation.show moreshow less

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Metadaten
Author:Karin Gotterbarm, Nicola Luckas, Oliver Höfert, Michael P. A. Lorenz, Regine Streber, Christian Papp, Francesc Viñes, Hans-Peter Steinrück, Andreas Görling
URN:urn:nbn:de:bvb:29-opus-38186
Document Type:Article
Language:English
Date of Publication (online):2012/11/08
Publishing Institution:Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU)
Release Date:2012/11/08
Tag:ab initio calculations; density functional theory; oxidation; palladium; reaction kinetics
SWD-Keyword:-
Original publication:Journal of Chemical Physics 136.9 (2012): 06.11.2012 <http://jcp.aip.org/resource/1/jcpsa6/v136/i9/p094702_s1>
Institutes:Naturwissenschaftliche Fakultät / Naturwissenschaftliche Fakultät -ohne weitere Spezifikation-
Dewey Decimal Classification:5 Naturwissenschaften und Mathematik / 54 Chemie / 540 Chemie und zugeordnete Wissenschaften
PACS-Classification:80.00.00 INTERDISCIPLINARY PHYSICS AND RELATED AREAS OF SCIENCE AND TECHNOLOGY / 82.00.00 Physical chemistry and chemical physics; Electronic structure theory of atoms and molecules, see 31.15.-p; Electronic structure theory of condensed matter, see section 71; Electronic structure theory for biomolecules, see 87.10.-e; Electronic structure of / 82.20.-w Chemical kinetics and dynamics / 82.20.Hf Product distribution (for state selected dynamics and product distribution, see 82.20.Bc)
80.00.00 INTERDISCIPLINARY PHYSICS AND RELATED AREAS OF SCIENCE AND TECHNOLOGY / 82.00.00 Physical chemistry and chemical physics; Electronic structure theory of atoms and molecules, see 31.15.-p; Electronic structure theory of condensed matter, see section 71; Electronic structure theory for biomolecules, see 87.10.-e; Electronic structure of / 82.20.-w Chemical kinetics and dynamics / 82.20.Rp State to state energy transfer (see also 31.70.Hq Time-dependent phenomena-in atomic and molecular physics)
80.00.00 INTERDISCIPLINARY PHYSICS AND RELATED AREAS OF SCIENCE AND TECHNOLOGY / 82.00.00 Physical chemistry and chemical physics; Electronic structure theory of atoms and molecules, see 31.15.-p; Electronic structure theory of condensed matter, see section 71; Electronic structure theory for biomolecules, see 87.10.-e; Electronic structure of / 82.30.-b Specific chemical reactions; reaction mechanisms / 82.30.Fi Ion-molecule, ion-ion, and charge-transfer reactions (see also 34.70.+e Charge transfer in atomic and molecular collisions); Charge transfer in enzymes, see 82.39.Jn and 87.15.R-
80.00.00 INTERDISCIPLINARY PHYSICS AND RELATED AREAS OF SCIENCE AND TECHNOLOGY / 82.00.00 Physical chemistry and chemical physics; Electronic structure theory of atoms and molecules, see 31.15.-p; Electronic structure theory of condensed matter, see section 71; Electronic structure theory for biomolecules, see 87.10.-e; Electronic structure of / 82.65.+r Surface and interface chemistry; heterogeneous catalysis at surfaces (for temporal and spatial patterns in surface reactions, see 82.40.Np; see also 82.45.Jn Surface structure, reactivity and catalysis in electrochemistry); Chemisorption/physisorption: ad
80.00.00 INTERDISCIPLINARY PHYSICS AND RELATED AREAS OF SCIENCE AND TECHNOLOGY / 82.00.00 Physical chemistry and chemical physics; Electronic structure theory of atoms and molecules, see 31.15.-p; Electronic structure theory of condensed matter, see section 71; Electronic structure theory for biomolecules, see 87.10.-e; Electronic structure of / 82.80.-d Chemical analysis and related physical methods of analysis (for related instrumentation, see section 07; for spectroscopic techniques in biological physics, see 87.64.-t) / 82.80.Pv Electron spectroscopy (X-ray photoelectron (XPS), Auger electron spectroscopy (AES), etc.)
Collections:Universität Erlangen-Nürnberg / Allianzlizenzen / Allianzlizenzen 2012

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