Synergistic effects in low-temperature CO oxidation on cerium oxide surfaces

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{
  "revision": 4, 
  "id": "2544", 
  "created": "2025-01-24T15:57:31.233380+00:00", 
  "metadata": {
    "doi": "10.24435/materialscloud:cc-jr", 
    "status": "published", 
    "title": "Synergistic effects in low-temperature CO oxidation on cerium oxide surfaces", 
    "mcid": "2025.21", 
    "license_addendum": null, 
    "_files": [
      {
        "description": "Readme file", 
        "key": "README.txt", 
        "size": 3067, 
        "checksum": "md5:ba64fe2a1ef89976fd656adca864fbec"
      }, 
      {
        "description": "Reaction path for the oxidation of CO to CO2 via the CO3 intermediate. The states a to g correspond to the intermediates along the reaction pathway.", 
        "key": "fig3.zip", 
        "size": 15894593, 
        "checksum": "md5:42a235cb0152ff0bcf00ec74752fe8bd"
      }, 
      {
        "description": "O2 adsorption on CeO2\u2212x(111) surfaces with (a-b) Vss and (c-d) Vs oxygen vacancies, and (f) Superoxo@Vss-II shown in (b) with co-adsorbed CO.", 
        "key": "fig4.zip", 
        "size": 3207800, 
        "checksum": "md5:c9711a1844b646478f1c0c30d0cc07e2"
      }, 
      {
        "description": "Reaction pathway for the oxidation of CO to CO2 via the intermediate O22\u207b species.", 
        "key": "fig5.zip", 
        "size": 16495690, 
        "checksum": "md5:b083672a84830c1804493ddb71071bab"
      }, 
      {
        "description": "Reaction path for the oxidation of CO to CO2 via the CO3 intermediate. The states a to g correspond to the intermediates along the reaction pathway.", 
        "key": "figS3.zip", 
        "size": 27113071, 
        "checksum": "md5:3e92e667fb01eb86eb67bd00a42603e6"
      }, 
      {
        "description": "Contains calculations for gas-phase molecules (CO2, CO, O2) and CeO2\u2212x surfaces with a subsurface oxygen vacancy and 2x2 periodicity.", 
        "key": "references.zip", 
        "size": 266270, 
        "checksum": "md5:7f19840f75d8cb9821727c06d72575aa"
      }
    ], 
    "owner": 64, 
    "_oai": {
      "id": "oai:materialscloud.org:2544"
    }, 
    "keywords": [
      "CO oxidation", 
      "Ceria", 
      "Peroxo and Superoxo", 
      "DFT"
    ], 
    "conceptrecid": "2543", 
    "is_last": true, 
    "references": [
      {
        "type": "Journal reference", 
        "doi": "10.xxxxxxxxxx", 
        "comment": "Paper where the data is discussed", 
        "citation": "P. G. Lustemberg, C. Yang, Y. Wang, M. V. Ganduglia-Pirovano, and C. W\u00f6lld, J. Am. Chem. Soc. xx, xxx-xxx (2025)"
      }
    ], 
    "publication_date": "Jan 28, 2025, 15:55:01", 
    "license": "Creative Commons Attribution 4.0 International", 
    "id": "2544", 
    "description": "The mechanisms underlying the reaction between carbon monoxide (CO) and activated dioxygen on metal oxide substrates to produce CO\u2082 remain poorly understood, particularly regarding the role of oxygen vacancies and the nature of the activated O\u2082 adsorbate. In this study, we present experimental findings from infrared reflection-absorption spectroscopy on a model system of bulk monocrystalline CeO\u2082(111). Contrary to expectations, exposing the reduced surface to dioxygen (O\u2082) at 80 K does not yield activated oxygen species, such as superoxo or peroxo. Notably, in the presence of adsorbed CO, an unexpected low-temperature oxidation reaction occurs, consuming CO while oxidizing the CeO\u2082 substrate. Since a direct reaction between impinging O\u2082 and adsorbed CO is unlikely at these low temperatures, a novel mechanism is proposed. Extensive spin-polarized density functional theory (DFT) calculations reveal that oxygen vacancies play a critical role in this low-temperature CO oxidation. Initially located in the subsurface region (Vss), these vacancies migrate to the surface (Vs) via a concerted interaction with coadsorbed CO and O\u2082, leading to O\u2082 activation and the formation of superoxo or peroxo species. Detailed analysis identifies key reaction intermediates and quantifies their adsorption energies and activation barriers. Our findings suggest that the peroxo-mediated pathway, with its lower activation barrier, is more favorable for CO oxidation at low temperatures compared to the carbonate pathway. This study provides valuable insights into the dynamic role of subsurface oxygen vacancies in the activation of gaseous O\u2082 and CO oxidation mechanisms on CeO\u2082.", 
    "version": 1, 
    "contributors": [
      {
        "email": "p.lustemberg@csic.es", 
        "affiliations": [
          "Institute of Catalysis and Petrochemistry, CSIC, 28049 Madrid, Spain"
        ], 
        "familyname": "Lustemberg", 
        "givennames": "Pablo G."
      }, 
      {
        "affiliations": [
          "State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China", 
          "School of Energy and Power Engineering, Beihang University, Beijing 100191, China"
        ], 
        "familyname": "Yang", 
        "givennames": "Chengwu"
      }, 
      {
        "affiliations": [
          "Institute of Functional Interfaces, IFG, Karlsruhe Institute of Technology, KIT, 76344 Eggenstein-Leopoldshafen, Germany"
        ], 
        "familyname": "Wang", 
        "givennames": "Yuemin"
      }, 
      {
        "affiliations": [
          "Institute of Catalysis and Petrochemistry, CSIC, 28049 Madrid, Spain"
        ], 
        "familyname": "Ganduglia-Pirovano", 
        "givennames": "M. Veronica"
      }, 
      {
        "affiliations": [
          "Institute of Functional Interfaces, IFG, Karlsruhe Institute of Technology, KIT, 76344 Eggenstein-Leopoldshafen, Germany"
        ], 
        "familyname": "W\u00f6ll", 
        "givennames": "Christof"
      }
    ], 
    "edited_by": 576
  }, 
  "updated": "2025-01-28T14:55:01.877841+00:00"
}