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Critical step in the HCl oxidation reaction over single-crystalline CeO2−x(111): Peroxo-induced site change of strongly adsorbed surface chlorine

Volkmar Koller1,2, Pablo G. Lustemberg3*, Alexander Spriewald-Luciano1,2, Sabrina M. Gericke4, Alfred Larsson5, Christian Sack1,2, Alexei Preobrajenski6, Edvin Lundgren5, M. Veronica Ganduglia-Pirovano3, Herbert Over1,2

1 Physical Chemistry Department, Justus-Liebig-University Giessen, Heinrich-Buff-Ring 17, 35392 Giessen, Germany

2 Center for Materials Research, Justus-Liebig-University Giessen, Heinrich-Buff-Ring 16, 35392 Giessen, Germany

3 Institute of Catalysis and Petrochemistry, ICP, Spanish National Research Council, CSIC, 28049 Madrid, Spain

4 Combustion Physics, Lund University, Box 118, 22100 Lund, Sweden

5 Synchrotron Radiation Research, Lund University, Box 118, 22100 Lund, Sweden

6 MAX IV Laboratory, Lund University, Box 118, 22100 Lund, Sweden

* Corresponding authors emails: p.lustemberg@csic.es
DOI10.24435/materialscloud:dq-1c [version v1]

Publication date: Sep 19, 2023

How to cite this record

Volkmar Koller, Pablo G. Lustemberg, Alexander Spriewald-Luciano, Sabrina M. Gericke, Alfred Larsson, Christian Sack, Alexei Preobrajenski, Edvin Lundgren, M. Veronica Ganduglia-Pirovano, Herbert Over, Critical step in the HCl oxidation reaction over single-crystalline CeO2−x(111): Peroxo-induced site change of strongly adsorbed surface chlorine, Materials Cloud Archive 2023.143 (2023), https://doi.org/10.24435/materialscloud:dq-1c


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, 287–297.], 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−x(111)-(√3 × √3)R30° 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 → 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−x(111) and is considered essential for understanding the function of ceria in oxidation catalysis.

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File name Size Description
2.9 KiB Contains the description of the data uploaded to the repository.
2.5 MiB O2-activation at 3Clvac- Ce3O5(111)-(3x3)
866.2 KiB Adsorbed peroxo(O2ads)and atomic oxygen on top of Ce atom (Otop).
4.6 MiB Re-oxidation process of 3Clvac-Ce3O5(111)-(3 x 3).
5.9 MiB De-chlorination process of 3Clvac-Ce3O5(111)-(3 x 3)
11.4 MiB States corresponding to the diffusion from a VSSS to VSS to VS vacancy in CeO2(111), Ce3O5(111) and 3Clvac/Ce3O5(111)
1.5 MiB O2 specie adsorbed as a peroxo o superoxo on 3Clvac/Ce3O5.
50.3 KiB Atomic coordinates of the de-chlorination process from two adsorbed O2 species and three Cl adsorbed on oxygen vacancies
1.5 MiB Initial state (IS) and final state (FS) connecting two peroxo states.
5.4 MiB States corresponding to Cl atoms at 1/3 ML, 2/3 ML, and 1 ML in the (√3 × √3)R30° with 3 oxygen vacancies.


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External references

Journal reference (Paper where the data is discussed)
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. XXX, XXX-XXX (2023) doi:10.1021/acscatal.3c03222


Deacon process reduced ceria peroxo surface species displacement of strongly adsorbed chlorine oxygen-induced de-chlorination process

Version history:

2023.143 (version v1) [This version] Sep 19, 2023 DOI10.24435/materialscloud:dq-1c