Critical step in the HCl oxidation reaction over single-crystalline CeO2−x(111): Peroxo-induced site change of strongly adsorbed surface chlorine
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{
"revision": 3,
"id": "1906",
"created": "2023-09-18T18:18:24.436790+00:00",
"metadata": {
"doi": "10.24435/materialscloud:dq-1c",
"status": "published",
"title": "Critical step in the HCl oxidation reaction over single-crystalline CeO2\u2212x(111): Peroxo-induced site change of strongly adsorbed surface chlorine",
"mcid": "2023.143",
"license_addendum": null,
"_files": [
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{
"description": "O2-activation at 3Clvac- Ce3O5(111)-(3x3)",
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"size": 2630053,
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{
"description": "Adsorbed peroxo(O2ads)and atomic oxygen on top of Ce atom (Otop).",
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{
"description": "Re-oxidation process of 3Clvac-Ce3O5(111)-(3 x 3).",
"key": "Figure8.zip",
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{
"description": "De-chlorination process of 3Clvac-Ce3O5(111)-(3 x 3)",
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{
"description": "States corresponding to the diffusion from a VSSS to VSS to VS vacancy in CeO2(111), Ce3O5(111) and 3Clvac/Ce3O5(111)",
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{
"description": "O2 specie adsorbed as a peroxo o superoxo on 3Clvac/Ce3O5.",
"key": "FigureS13.zip",
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{
"description": "Atomic coordinates of the de-chlorination process from two adsorbed O2 species and three Cl adsorbed on oxygen vacancies",
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{
"description": "Initial state (IS) and final state (FS) connecting two peroxo states.",
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{
"description": "States corresponding to Cl atoms at 1/3 ML, 2/3 ML, and 1 ML in the (\u221a3 \u00d7 \u221a3)R30\u00b0 with 3 oxygen vacancies.",
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"owner": 64,
"_oai": {
"id": "oai:materialscloud.org:1906"
},
"keywords": [
"Deacon process",
"reduced ceria",
"peroxo surface species",
"displacement of strongly adsorbed chlorine",
"oxygen-induced de-chlorination process"
],
"conceptrecid": "1905",
"is_last": true,
"references": [
{
"type": "Journal reference",
"doi": "10.1021/acscatal.3c03222",
"comment": "Paper where the data is discussed",
"citation": "V. Koller, P. Lustemberg, A. Spriewald-Luciano, S. Gericke, A. Larsson, C. Sack, A. Preobrajenski, E. Lundgren, M. V. Ganduglia-Pirovano, H. Over, ACS Catal. 13, 12994\u221213007 (2023)"
}
],
"publication_date": "Sep 19, 2023, 11:11:36",
"license": "Creative Commons Attribution 4.0 International",
"id": "1906",
"description": "The catalytic oxidation of HCl by molecular oxygen (Deacon process) over ceria allows the recovery of molecular chlorine from omnipresent HCl waste produced in various industrial processes. In previous density functional theory (DFT) model calculations by Amrute et al. [J. Catal. 2012, 286, 287\u2013297.], it was proposed that the most critical reaction step in this process is the displacement of tightly bound chlorine at a vacant oxygen position on the CeO2(111) surface (Clvac) toward a less strongly bound cerium on-top (Cltop) position. This step is highly endothermic by more than 2 eV. On the basis of a dedicated model study, namely the re-oxidation of a chlorinated single crystalline Clvac-CeO2\u2212x(111)-(\u221a3 \u00d7 \u221a3)R30\u00b0 surface structure, we provide in-situ synchrotron-based spectroscopic data (high-resolution core level spectroscopy (HRCLS) and X-ray adsorption near edge structure (XANES)) for this oxygen-induced de-chlorination process. Combined with theoretical evidence from DFT calculations, the Clvac \u2192 Cltop displacement reaction is predicted to be induced by an adsorbed peroxo species (O22-), making the displacement step concerted and exothermic by only 0.6 eV with an activation barrier of only 1.04 eV. The peroxo species is shown to be important for the re-oxidation of Clvac-CeO2\u2212x(111) and is considered essential for understanding the function of ceria in oxidation catalysis.",
"version": 1,
"contributors": [
{
"affiliations": [
"Physical Chemistry Department, Justus-Liebig-University Giessen, Heinrich-Buff-Ring 17, 35392 Giessen, Germany",
"Center for Materials Research, Justus-Liebig-University Giessen, Heinrich-Buff-Ring 16, 35392 Giessen, Germany"
],
"familyname": "Koller",
"givennames": "Volkmar"
},
{
"email": "p.lustemberg@csic.es",
"affiliations": [
"Institute of Catalysis and Petrochemistry, ICP, Spanish National Research Council, CSIC, 28049 Madrid, Spain"
],
"familyname": "Lustemberg",
"givennames": "Pablo G."
},
{
"affiliations": [
"Physical Chemistry Department, Justus-Liebig-University Giessen, Heinrich-Buff-Ring 17, 35392 Giessen, Germany",
"Center for Materials Research, Justus-Liebig-University Giessen, Heinrich-Buff-Ring 16, 35392 Giessen, Germany"
],
"familyname": "Spriewald-Luciano",
"givennames": "Alexander"
},
{
"affiliations": [
"Combustion Physics, Lund University, Box 118, 22100 Lund, Sweden"
],
"familyname": "Gericke",
"givennames": "Sabrina M."
},
{
"affiliations": [
"Synchrotron Radiation Research, Lund University, Box 118, 22100 Lund, Sweden"
],
"familyname": "Larsson",
"givennames": "Alfred"
},
{
"affiliations": [
"Physical Chemistry Department, Justus-Liebig-University Giessen, Heinrich-Buff-Ring 17, 35392 Giessen, Germany",
"Center for Materials Research, Justus-Liebig-University Giessen, Heinrich-Buff-Ring 16, 35392 Giessen, Germany"
],
"familyname": "Sack",
"givennames": "Christian"
},
{
"affiliations": [
"MAX IV Laboratory, Lund University, Box 118, 22100 Lund, Sweden"
],
"familyname": "Preobrajenski",
"givennames": "Alexei"
},
{
"affiliations": [
"Synchrotron Radiation Research, Lund University, Box 118, 22100 Lund, Sweden"
],
"familyname": "Lundgren",
"givennames": "Edvin"
},
{
"affiliations": [
"Institute of Catalysis and Petrochemistry, ICP, Spanish National Research Council, CSIC, 28049 Madrid, Spain"
],
"familyname": "Ganduglia-Pirovano",
"givennames": "M. Veronica"
},
{
"affiliations": [
"Physical Chemistry Department, Justus-Liebig-University Giessen, Heinrich-Buff-Ring 17, 35392 Giessen, Germany",
"Center for Materials Research, Justus-Liebig-University Giessen, Heinrich-Buff-Ring 16, 35392 Giessen, Germany"
],
"familyname": "Over",
"givennames": "Herbert"
}
],
"edited_by": 64
},
"updated": "2024-08-02T14:53:13.132149+00:00"
}