{
  "abstract": "Electrochemical conversion of methane into liquid oxygenates has attracted significant attention as a sustainable process for the valorization of natural gas. Platinum single crystals provide well-defined model surfaces for mechanistic studies of methane oxidation via direct activation, with Pt(100) being the only facet capable of catalyzing this reaction. Here, we combine electrochemical measurements and theoretical calculations to investigate how the microenvironment at the Pt(100) electrode interface influences methane activation. We first confirm the crucial role of (100) terraces as the main active sites by using electrodes with different degrees of surface order, obtained by cooling them under different atmospheres. Cyclic voltammetry further reveals that methane dissolved in the electrolyte can be activated only at potentials between 0.30–0.60 V vs RHE, a window in which OH species are co-adsorbed on the electrode surface in acidic media. In contrast, more alkaline electrolytes inhibit the overall reaction. Density functional theory calculations show that interfacial OH directs methane activation toward either OH-mediated or surface-mediated C–H abstraction, with activation barriers of 1.0 and 0.6 eV, respectively. By accounting for the co-presence of adsorbed OH during methane activation, our results provide a more realistic description of the electrochemical interface and rationalize the pronounced structure sensitivity of methane activation on platinum surfaces.",
  "abstract_shown": true,
  "affiliations": [
    "Catalan Institute of Nanoscience and Nanotechnology (ICN2), CSIC and Barcelona Institute of Science and Technology, UAB Campus, 08193 Bellaterra, Barcelona, Spain",
    "Department of Chemistry, Simon Fraser University, 8888 University Drive, Burnaby, British Columbia, Canada, V5A 1S6",
    "Instituto de Eletroquı́mica, Universidad de Alicante, Apdo. 99, Alicante, Spain, E-03080",
    "Catalan Institution for Research and Advanced Studies (ICREA)"
  ],
  "article_type": null,
  "arxiv": null,
  "author_total": 6,
  "authors": [
    {
      "affs": [
        0
      ],
      "name": "Gabriele Cioli"
    },
    {
      "affs": [
        1
      ],
      "name": "Rebecca Gerber"
    },
    {
      "affs": [
        2
      ],
      "name": "Rubén Rizo"
    },
    {
      "affs": [
        2
      ],
      "name": "José Solla-Gullón"
    },
    {
      "affs": [
        1
      ],
      "name": "Samira Siahrostami"
    },
    {
      "affs": [
        0,
        3
      ],
      "name": "Marı́a Escudero-Escribano"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/4sxp4zea48wa9.bib",
  "cited_by": 0,
  "doi": "10.26434/chemrxiv.15008150/v1",
  "fulltext_url": null,
  "id": "4sxp4zea48wa9",
  "issns": [],
  "landing_url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008150/v1",
  "language": null,
  "licence": "CC-BY",
  "licence_label": "CC BY",
  "licence_source": "journal",
  "licence_url": "https://creativecommons.org/licenses/by/4.0/",
  "metadata_licence": null,
  "native_subjects": [
    [
      "openalex",
      "2105|Electrocatalysts for Energy Conversion"
    ]
  ],
  "openalex": "W7204946459",
  "pdf_url": "https://chemrxiv.org/doi/pdf/10.26434/chemrxiv.15008150/v1",
  "pmcid": null,
  "pmid": null,
  "published": "2026-09-01",
  "publisher": "American Chemical Society (ACS)",
  "ris": "https://research.draconitic.com/paper/4sxp4zea48wa9.ris",
  "sources": [
    {
      "first_seen": "2026-10-30T12:17:17Z",
      "native_id": "10.26434/chemrxiv.15008150",
      "source": "chemrxiv",
      "url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008150/v1"
    }
  ],
  "subjects": [
    {
      "field": "chemistry",
      "origin": "openalex:2105|Electrocatalysts for Energy Conversion",
      "subfield": "electrochemistry-energy"
    }
  ],
  "title": "Interfacial Microenvironment on Pt(100) Controls Electrochemical Methane Activation",
  "title_text": "Interfacial Microenvironment on Pt(100) Controls Electrochemical Methane Activation",
  "type": "preprint",
  "updated_at": "2026-10-30T12:17:17Z",
  "url": "https://research.draconitic.com/paper/4sxp4zea48wa9",
  "venue": "ChemRxiv",
  "versions": []
}