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PreprintCC BYChemRxiv

Interfacial Microenvironment on Pt(100) Controls Electrochemical Methane Activation

  • Gabriele Cioli1
  • Rebecca Gerber2
  • Rubén Rizo3
  • José Solla-Gullón3
  • Samira Siahrostami2
  • Marı́a Escudero-Escribano1,4
4 affiliations
  1. 1Catalan Institute of Nanoscience and Nanotechnology (ICN2), CSIC and Barcelona Institute of Science and Technology, UAB Campus, 08193 Bellaterra, Barcelona, Spain
  2. 2Department of Chemistry, Simon Fraser University, 8888 University Drive, Burnaby, British Columbia, Canada, V5A 1S6
  3. 3Instituto de Eletroquı́mica, Universidad de Alicante, Apdo. 99, Alicante, Spain, E-03080
  4. 4Catalan Institution for Research and Advanced Studies (ICREA)
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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.

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Cite

BibTeXRIS
BibTeX
@misc{cioli2026interfacial,
  title = {{Interfacial Microenvironment on Pt(100) Controls Electrochemical Methane Activation}},
  author = {Gabriele Cioli and Rebecca Gerber and Rubén Rizo and José Solla-Gullón and Samira Siahrostami and Marı́a Escudero-Escribano},
  howpublished = {ChemRxiv},
  year = {2026},
  month = sep,
  doi = {10.26434/chemrxiv.15008150/v1},
  url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008150/v1},
  note = {CC BY},
}
RIS
TY  - UNPB
TI  - Interfacial Microenvironment on Pt(100) Controls Electrochemical Methane Activation
AU  - Gabriele Cioli
AU  - Rebecca Gerber
AU  - Rubén Rizo
AU  - José Solla-Gullón
AU  - Samira Siahrostami
AU  - Marı́a Escudero-Escribano
PY  - 2026
DA  - 2026/09/01
PB  - ChemRxiv
DO  - 10.26434/chemrxiv.15008150/v1
UR  - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008150/v1
AB  - 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.
ER  -