Tuning selectivity in the direct conversion of methane to methanol: bimetallic synergistic effects on the cleavage of C-H and O-H bonds over NiCu/CeO₂ catalysts


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{
  "revision": 6, 
  "metadata": {
    "publication_date": "Jun 10, 2022, 21:19:16", 
    "_oai": {
      "id": "oai:materialscloud.org:1376"
    }, 
    "license": "Creative Commons Attribution 4.0 International", 
    "description": "The efficient activation of methane and simultaneous water dissociation are crucial in many catalytic reactions on oxide-supported transition metal catalysts. On very low-loaded Ni/CeO\u2082 surfaces, methane easily fully decomposes, CH\u2084 -> C + 4H,  and water dissociates, H\u2082O -> OH + H. However, in important reactions such as the direct oxidation of methane to methanol (MTM), where complex interplay exists between reactants (CH\u2084, O\u2082), it is desirable to avoid the complete dehydrogenation of methane to carbon.  Remarkably, the barrier for the activation of C-H bonds in CHx (x= 1-3) species on Ni/CeO\u2082 surfaces can be manipulated by adding Cu, forming bimetallic NiCu clusters, whereas the ease for cleavage of O-H bonds in water, is not affected by ensemble effects, as obtained from density functional theory-based calculations. CH4 activation occurs only on Ni sites and H\u2082O activation on both Ni and Cu sites. The MTM reaction pathway for the example of the Ni\u2083Cu\u2081/CeO\u2082 model catalyst predict higher selectivity and a lower activation barrier for methanol production, compared with that for Ni\u2084-CeO\u2082. These findings point toward a possible strategy to design active and stable catalysts which can be employed for methane activation and conversions.", 
    "contributors": [
      {
        "familyname": "Lustemberg", 
        "affiliations": [
          "Institute of Catalysis and Petrochemistry, ICP, Spanish National Research Council, CSIC, 28049 Madrid, Spain", 
          "Institute of Physics Rosario, IFIR, National Scientific and Technical Research Council, CONICET,  S2000EKF Rosario, Santa Fe, Argentina"
        ], 
        "email": "p.lustemberg@csic.es", 
        "givennames": "Pablo G."
      }, 
      {
        "familyname": "Senanayake", 
        "affiliations": [
          "Chemistry Division, Brookhaven National Laboratory, Upton, New York 11973, United States"
        ], 
        "givennames": "Sanjaya D."
      }, 
      {
        "familyname": "Rodriguez", 
        "affiliations": [
          "Chemistry Division, Brookhaven National Laboratory, Upton, New York 11973, United States"
        ], 
        "givennames": "Jose A."
      }, 
      {
        "familyname": "Ganduglia-Pirovano", 
        "affiliations": [
          "Institute of Catalysis and Petrochemistry, ICP, Spanish National Research Council, CSIC, 28049 Madrid, Spain"
        ], 
        "email": "vgp@icp.csic.es", 
        "givennames": "M. Ver\u00f3nica"
      }
    ], 
    "edited_by": 64, 
    "title": "Tuning selectivity in the direct conversion of methane to methanol: bimetallic synergistic effects on the cleavage of C-H and O-H bonds over NiCu/CeO\u2082 catalysts", 
    "conceptrecid": "1375", 
    "license_addendum": null, 
    "doi": "10.24435/materialscloud:8y-7m", 
    "mcid": "2022.75", 
    "_files": [
      {
        "size": 50811, 
        "key": "CH4gas_H2Ogas.zip", 
        "checksum": "md5:501c7dea6db8deeef6162062c9455db9", 
        "description": "DFT calculations of CH4 and H2O in gas phase"
      }, 
      {
        "size": 13933786, 
        "key": "Models.zip", 
        "checksum": "md5:5a629881cfc183e3e89f69d070d4160e", 
        "description": "Includes the DFT calculations of the following surfaces models: Cu(111), Ni(111), Cu4.CeO2, Ni4.CeO2, Ni1Cu3.CeO2, Ni2Cu2.CeO2 and Ni3Cu1.CeO2"
      }, 
      {
        "size": 175665362, 
        "key": "Methane_Activation.zip", 
        "checksum": "md5:9eecf45c554a05ea75a663e7ec1981a1", 
        "description": "Includes the DFT calculations of Methane adsorption and activation on: Cu(111), Ni(111), Cu4.CeO2, Ni4.CeO2, Ni1Cu3.CeO2, Ni2Cu2.CeO2 and Ni3Cu1.CeO2. Also, the intermediate states of the complete decomposition of CH4 are found."
      }, 
      {
        "size": 3524622, 
        "key": "Hydrogen_Adsorption.zip", 
        "checksum": "md5:38367b56da2d1683be45c1dbb6faf4c0", 
        "description": "Includes the DFT calculations of Hydrogen atom adsorbed on: Cu4.CeO2, Ni4.CeO2, Ni1Cu3.CeO2, Ni2Cu2.CeO2 and Ni3Cu1.CeO2"
      }, 
      {
        "size": 59260101, 
        "key": "Water_Activation.zip", 
        "checksum": "md5:3adf06bcc3fd96895eb1277f8423d0f8", 
        "description": "Includes the DFT calculations of Water adsorption and activation on: Cu(111), Ni(111), Cu4.CeO2, Ni4.CeO2, Ni1Cu3.CeO2, Ni2Cu2.CeO2 and Ni3Cu1.CeO2"
      }, 
      {
        "size": 95574289, 
        "key": "Methanol_Formation.zip", 
        "checksum": "md5:83af6eb1ea86cbf00b5564710d0a7e6d", 
        "description": "It contains all the relevant states for the formation of methanol from CH4 and O adsorbed on the Ni4.CeO2 and Ni3Cu1.CeO2 surfaces (see Figure 4 of the manuscript)."
      }, 
      {
        "size": 2409, 
        "key": "README.txt", 
        "checksum": "md5:b2d37dc24276d9e3c49367d3dde10f06", 
        "description": "Readme file with the relevant data description"
      }
    ], 
    "id": "1376", 
    "keywords": [
      "bimetallic", 
      "ceria", 
      "methane activation", 
      "water activation"
    ], 
    "is_last": true, 
    "status": "published", 
    "references": [
      {
        "doi": "10.1021/acs.jpclett.2c00885", 
        "url": "https://pubs.acs.org/doi/10.1021/acs.jpclett.2c00885", 
        "comment": "Paper in which the data is described and analysed", 
        "type": "Journal reference", 
        "citation": "P. G. Lustemberg, S. D. Senanayake, J. A. Rodriguez, M. V. Ganduglia-Pirovano, J. Phys. Chem. Lett. 13, 24, 5589\u20135596 (2022)"
      }
    ], 
    "version": 1, 
    "owner": 64
  }, 
  "id": "1376", 
  "created": "2022-06-07T20:55:36.811521+00:00", 
  "updated": "2022-07-07T21:24:51.388001+00:00"
}