From Methane to Methanol: Pd-iC-CeO2 Catalysts Engineered for High Selectivity via Mechano-Chemical Synthesis

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{
  "metadata": {
    "edited_by": 98, 
    "owner": 64, 
    "_oai": {
      "id": "oai:materialscloud.org:2281"
    }, 
    "description": "In the pursuit of selective conversion of methane directly to methanol in the liquid phase, a common challenge is the concurrent formation of undesirable liquid oxygenates or combustion byproducts. However, we demonstrate that monometallic Pd-CeO2 catalysts, modified by carbon, created by a simple mechanochemical synthesis method exhibit 100% selectivity towards methanol at 75\u00b0C, using hydrogen peroxide as oxidizing agent. The solvent-free synthesis yields a distinctive Pd-iC-CeO2 interface, where interfacial carbon (iC) modulates metal-oxide interactions and facilitates tandem methane activation and peroxide decomposition, thus resulting in an exclusive methanol selectivity of 100% with a rate of 117 \u00b5mol/gcat at 75\u00b0C. Notably, solvent interactions of H2O2 (aq) were found to be critical for methanol selectivity through a DFT-simulated Eley-Rideal-like mechanism. This mechanism uniquely enables the direct conversion of methane into methanol via a solid-liquid-gas process.", 
    "mcid": "2024.117", 
    "id": "2281", 
    "license": "Creative Commons Attribution 4.0 International", 
    "license_addendum": null, 
    "references": [
      {
        "citation": "J. D. Jim\u00e9nez, P. G. Lustemberg, M. Danielis, E. Fern\u00e1ndez-Villanueva, S. Hwang, I. Waluyo, A. Hunt, D. Wierzbicki, J. Zhang, L. Qi, A. Trovarelli, J. A. Rodriguez, S. Colussi, M. V. Ganduglia-Pirovano, S. D. Senanayake, J. Am. Chem. Soc, XX, XXX-XXX (2024)", 
        "type": "Journal reference"
      }
    ], 
    "doi": "10.24435/materialscloud:dz-zz", 
    "keywords": [
      "Pd.CeO2", 
      "PdC.CeO2", 
      "CH4", 
      "CH3OH", 
      "H2O2", 
      "Eley-Rideal mechanism"
    ], 
    "contributors": [
      {
        "affiliations": [
          "Chemistry Division, Brookhaven National Laboratory, Upton, NY, 11973, USA"
        ], 
        "familyname": "Jim\u00e9nez", 
        "givennames": "Juan D."
      }, 
      {
        "affiliations": [
          "Institute of Catalysis and Petrochemistry, ICP, Spanish National Research Council, CSIC, 28049 Madrid, Spain"
        ], 
        "familyname": "Lustemberg", 
        "email": "p.lustemberg@csic.es", 
        "givennames": "Pablo G."
      }, 
      {
        "affiliations": [
          "Polytechnic Department, University of Udine and INSTM, Via del Cotonificio 108, 33100 Udine"
        ], 
        "familyname": "Danielis", 
        "givennames": "Maila"
      }, 
      {
        "affiliations": [
          "Institute of Catalysis and Petrochemistry, ICP, Spanish National Research Council, CSIC, 28049 Madrid, Spain", 
          "Universitat Polit\u00e8cnica de Val\u00e8ncia, Cam\u00ed de Vera s/n, 46022, Val\u00e8ncia, Spain"
        ], 
        "familyname": "Fern\u00e1ndez-Villanueva", 
        "givennames": "Estefan\u00eda"
      }, 
      {
        "affiliations": [
          "Center for Functional Nanomaterials, Brookhaven National Laboratory, Upton, NY, 11973, USA"
        ], 
        "familyname": "Hwang", 
        "givennames": "Sooyeon"
      }, 
      {
        "affiliations": [
          "National Synchrotron Light Source II, Brookhaven National Laboratory, Upton, New York 11973, USA"
        ], 
        "familyname": "Waluyo", 
        "givennames": "Iradwikanari"
      }, 
      {
        "affiliations": [
          "National Synchrotron Light Source II, Brookhaven National Laboratory, Upton, New York 11973, USA"
        ], 
        "familyname": "Hunt", 
        "givennames": "Adrian"
      }, 
      {
        "affiliations": [
          "National Synchrotron Light Source II, Brookhaven National Laboratory, Upton, New York 11973, USA"
        ], 
        "familyname": "Wierzbicki", 
        "givennames": "Dominik"
      }, 
      {
        "affiliations": [
          "Ames National Laboratory, Iowa State University, Ames, Iowa, 50011, USA"
        ], 
        "familyname": "Zhang", 
        "givennames": "Jie"
      }, 
      {
        "affiliations": [
          "Ames National Laboratory, Iowa State University, Ames, Iowa, 50011, USA"
        ], 
        "familyname": "Qi", 
        "givennames": "Long"
      }, 
      {
        "affiliations": [
          "Polytechnic Department, University of Udine and INSTM, Via del Cotonificio 108, 33100 Udine"
        ], 
        "familyname": "Trovarelli", 
        "givennames": "Alessandro"
      }, 
      {
        "affiliations": [
          "Chemistry Division, Brookhaven National Laboratory, Upton, NY, 11973, USA", 
          "Department of Chemistry, State University of New York Stony Brook, Stony Brook, NY 11794, USA"
        ], 
        "familyname": "Rodriguez", 
        "givennames": "Jose A."
      }, 
      {
        "affiliations": [
          "Polytechnic Department, University of Udine and INSTM, Via del Cotonificio 108, 33100 Udine"
        ], 
        "familyname": "Colussi", 
        "givennames": "Sara"
      }, 
      {
        "affiliations": [
          "Institute of Catalysis and Petrochemistry, ICP, Spanish National Research Council, CSIC, 28049 Madrid, Spain"
        ], 
        "familyname": "Ganduglia-Pirovano", 
        "givennames": "M. Ver\u00f3nica"
      }, 
      {
        "affiliations": [
          "Chemistry Division, Brookhaven National Laboratory, Upton, NY, 11973, USA"
        ], 
        "familyname": "Senanayake", 
        "givennames": "Sanjaya D."
      }
    ], 
    "conceptrecid": "2280", 
    "version": 1, 
    "publication_date": "Aug 06, 2024, 09:49:28", 
    "is_last": true, 
    "status": "published", 
    "_files": [
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        "size": 6429030, 
        "checksum": "md5:a4d3b68b3d8fd790c1e10abc2a1b2ce4", 
        "description": "This file includes the DFT calculations for two catalysts, Pd.CeO2 and PdiC.CeO2, as well as the molecules CH4, H2O2, and CH3OH in the gas phase.", 
        "key": "references.zip"
      }, 
      {
        "size": 57538912, 
        "checksum": "md5:83f66b825abb8454938d7a25257afb59", 
        "description": "Contains the adsorbed molecular state of CH4 and the dissociated state of CH3+H on each catalyst", 
        "key": "CH4_activation.zip"
      }, 
      {
        "size": 45390441, 
        "checksum": "md5:f8afeaf5fc418bc9ef8cbebc24c883ff", 
        "description": "Includes the adsorbed molecular state of H2O2 and the dissociated state of OOH+H on each catalyst", 
        "key": "H2O2_activation.zip"
      }, 
      {
        "size": 233610454, 
        "checksum": "md5:cc80cccc71c96bc73f35841b2e180f57", 
        "description": "Features the stable states considered through the Langmuir-Hinshelwood mechanism on each catalyst, corresponding to the two mechanisms shown in Figure 8. There are six states for PdiC.CeO2 with folders named A to F, and nine states for Pd.CeO2 with folders named a to i.", 
        "key": "Langmuir-Hinshelwood_mechanism.zip"
      }, 
      {
        "size": 205999985, 
        "checksum": "md5:90dadc7c978402096dbfbdfdc34b6ad4", 
        "description": "Contains the stable states considered through the Langmuir-Hinshelwood mechanism for each catalyst, corresponding to the two mechanisms in Figure 9. There are three states, a, b, and c for PdiC.CeO2, and A, B, and C for Pd.CeO2.", 
        "key": "Eley-Rideal_mechanism.zip"
      }, 
      {
        "size": 1853, 
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        "description": "Readme file, includes tge description of the uploaded data", 
        "key": "README.txt"
      }
    ], 
    "title": "From Methane to Methanol: Pd-iC-CeO2 Catalysts Engineered for High Selectivity via Mechano-Chemical Synthesis"
  }, 
  "id": "2281", 
  "updated": "2024-08-06T07:49:28.554634+00:00", 
  "created": "2024-08-02T14:48:36.448477+00:00", 
  "revision": 5
}