{
  "abstract": "Electrochemical reaction rates are controlled by both interfacial charge-transfer kinetics and reactive-ion transport. In charged porous media, fixed charges enrich reactive counterions near pore walls, enabling transport beyond the classical diffusion limit via surface conduction (SC). Under overlimiting conditions, classical Butler-Volmer kinetics predict indefinitely increasing current with overpotential, contrasting with microscopic electron-transfer theories, which impose a finite reaction-limited current. Here, we couple the one-dimensional leaky membrane model to coupled ion-electron transfer (CIET) kinetics to examine the interplay between transport and reaction limitations. The limiting behavior is governed by the scaled surface charge $(\\tildeρ_s)$ and a Damköhler number $(Da)$ comparing reaction-limited and diffusion-limited currents. We derive analytical limiting-current expressions for neutral, positive, and negatively charged porous media, mapping underlimiting-to-overlimiting transitions in the $(Da,\\tildeρ_s)$ plane. By preventing reactive-ion depletion, SC restores polarization-curve sensitivity to charge-transfer kinetics that would otherwise be obscured by diffusion limitation. Fitting to published Cu electrodeposition data in charged AAO membranes yields $Da\\approx24$. CIET parameters fitted to AAO($-$) also describe AAO($+$) and predict a finite AAO($-$) reaction limit beyond the applied voltage range. These results provide a framework for distinguishing transport-limited and reaction-limited responses in electrochemical systems and establish charged porous media as platforms to reveal electrochemical reaction-kinetic descriptors.",
  "abstract_shown": true,
  "affiliations": [],
  "article_type": null,
  "arxiv": "2609.03146",
  "author_total": 3,
  "authors": [
    {
      "name": "Arjun V. Yennemadi"
    },
    {
      "name": "Junghyun Yoon"
    },
    {
      "name": "Martin Z. Bazant"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/6z38gj3y074rh.bib",
  "cited_by": 0,
  "doi": "10.48550/arxiv.2609.03146",
  "fulltext_url": null,
  "id": "6z38gj3y074rh",
  "issns": [],
  "landing_url": "https://arxiv.org/abs/2609.03146",
  "language": null,
  "licence": "CC-BY-4.0",
  "licence_label": "CC BY 4.0",
  "licence_source": "article",
  "licence_url": "http://creativecommons.org/licenses/by/4.0/",
  "metadata_licence": "CC0-1.0",
  "native_subjects": [
    [
      "arxiv",
      "physics.chem-ph"
    ]
  ],
  "openalex": null,
  "pdf_url": "https://arxiv.org/pdf/2609.03146",
  "pmcid": null,
  "pmid": null,
  "published": "2026-09-02",
  "publisher": null,
  "ris": "https://research.draconitic.com/paper/6z38gj3y074rh.ris",
  "sources": [
    {
      "first_seen": "2026-10-30T12:18:31Z",
      "native_id": "2609.03146",
      "source": "arxiv",
      "url": "https://arxiv.org/abs/2609.03146"
    }
  ],
  "subjects": [
    {
      "field": "chemistry",
      "origin": "arxiv:physics.chem-ph",
      "subfield": "physical"
    }
  ],
  "title": "Overlimiting Ion Transport and Reaction Limitations in Charged Porous Media",
  "title_text": "Overlimiting Ion Transport and Reaction Limitations in Charged Porous Media",
  "type": "preprint",
  "updated_at": "2026-10-30T12:18:31Z",
  "url": "https://research.draconitic.com/paper/6z38gj3y074rh",
  "venue": "arXiv",
  "versions": []
}