{
  "abstract": "This study establishes an in situ synchrotron approach to directly link molten-salt chemistry, redox-buffer speciation, and alloy corrosion in chloride melts. Using a first-of-its-kind corrosion cell coupled to simultaneous X-ray absorption spectroscopy (XAS) and X-ray fluorescence (XRF), we monitor europium redox-buffer speciation and chromium dissolution during corrosion of Ni-20Cr in molten LiCl-KCl and KCl-MgCl2 salts. To build a mechanistic framework, we combine UV-vis optical basicity measurements, in situ electrochemistry, and molecular dynamics simulations to quantify how salt chlorobasicity reshapes europium solvation and shifts the Eu(III)/Eu(II) apparent potential. Increasing MgCl2 content drives the apparent potential of the Eu(III)/Eu(II) couple +0.49 V relative to LiCl-KCl and stabilizes Eu(II)-compatible solvation environments. In situ, time-resolved Eu L3-edge XANES reveals progressive Eu(III) reduction in KCl-MgCl2 melts, while Eu(III) remains predominantly stable in LiCl-KCl. This behavior is consistent with a chlorobasicity-activated reaction with boron nitride (BN) cell components. In less chlorobasic melts, salt redox chemistry enables BN chlorination, allowing BN to act as a sacrificial reductant and chlorinating agent that promotes Eu(III) to Eu(II) conversion, whereas this pathway is not thermodynamically favored in LiCl-KCl. During active corrosion of Ni-20Cr, coupled Eu XANES and Cr XRF measurements show concurrent Eu(III) to Eu(II) conversion and Cr dissolution, confirming that Eu(III) is the oxidizing species driving chromium oxidation. Together, these results demonstrate that chlorobasicity is a central control variable for redox-buffer speciation and corrosion thermodynamics, and more broadly that chlorobasicity can enable or suppress reactive pathways with structural materials in high-temperature molten salts.",
  "abstract_shown": true,
  "affiliations": [
    "Department of Nuclear Engineering and Engineering Physics, University of Wisconsin-Madison, Madison, Wisconsin53706, United States.",
    "Chemistry Division, Brookhaven National Laboratory, Upton, New York11973, United States.",
    "Department of Chemistry, University of Tennessee-Knoxville, Knoxville, Tennessee37996, United States.",
    "Department of Material Science and Chemical Engineering, Stony Brook University, Stony Brook, New York11794, United States.",
    "Chemical Sciences Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee37830, United States.",
    "6IJCLab, CNRS/IN2P3, Université Paris-Saclay, 91405Orsay, France.",
    "National Synchrotron Light Source-II, Brookhaven National Laboratory, Upton, New York11973, United States."
  ],
  "article_type": "research article",
  "arxiv": null,
  "author_total": 18,
  "authors": [
    {
      "affs": [
        0
      ],
      "name": "Kailee Buttice",
      "orcid": "0000-0002-8666-4275"
    },
    {
      "affs": [
        0
      ],
      "name": "Bonita Goh"
    },
    {
      "affs": [
        1
      ],
      "name": "Matthew S Emerson",
      "orcid": "0000-0001-7801-4734"
    },
    {
      "affs": [
        2
      ],
      "name": "Ellie Kim",
      "orcid": "0000-0003-4906-1261"
    },
    {
      "affs": [
        3
      ],
      "name": "Yuxiang Peng",
      "orcid": "0000-0002-8688-3654"
    },
    {
      "affs": [
        1
      ],
      "name": "Bobby Layne"
    },
    {
      "affs": [
        0
      ],
      "name": "Isabelle Baggenstoss"
    },
    {
      "affs": [
        0
      ],
      "name": "Shea McCarthy"
    },
    {
      "affs": [
        0
      ],
      "name": "George Vukovic"
    },
    {
      "affs": [
        0
      ],
      "name": "Changkyu Kim",
      "orcid": "0000-0002-9050-6309"
    },
    {
      "affs": [
        0
      ],
      "name": "Jagadeesh Sure"
    },
    {
      "affs": [
        2,
        4
      ],
      "name": "Sheng Dai",
      "orcid": "0000-0002-8046-3931"
    },
    {
      "affs": [
        5
      ],
      "name": "Céline Cannes",
      "orcid": "0000-0003-4788-5072"
    },
    {
      "affs": [
        5
      ],
      "name": "Sylvie Delpech"
    },
    {
      "affs": [
        1
      ],
      "name": "James F Wishart",
      "orcid": "0000-0002-0488-7636"
    },
    {
      "affs": [
        4
      ],
      "name": "Santanu Roy",
      "orcid": "0000-0001-6991-8205"
    },
    {
      "affs": [
        3,
        6
      ],
      "name": "Yu-Chen Karen Chen-Wiegart",
      "orcid": "0000-0003-4445-2159"
    },
    {
      "affs": [
        0
      ],
      "name": "Adrien Couet",
      "orcid": "0000-0002-7330-5150"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/352q6feb8vz8t.bib",
  "cited_by": 1,
  "doi": "10.1021/jacs.6c11331",
  "fulltext_url": "https://europepmc.org/articles/PMC13721176",
  "id": "352q6feb8vz8t",
  "issns": [
    "0002-7863",
    "1520-5126"
  ],
  "landing_url": "https://europepmc.org/article/MED/42954569",
  "language": "eng",
  "licence": "CC-BY",
  "licence_label": "CC BY",
  "licence_source": "article",
  "licence_url": "https://creativecommons.org/licenses/by/4.0/",
  "metadata_licence": null,
  "native_subjects": [
    [
      "heading",
      "Article"
    ],
    [
      "openalex",
      "1507|Molten salt chemistry and electrochemical processes"
    ]
  ],
  "openalex": "W7162285505",
  "pdf_url": "https://europepmc.org/articles/PMC13721176?pdf=render",
  "pmcid": "PMC13721176",
  "pmid": "42954569",
  "published": "2026-10-01",
  "publisher": null,
  "ris": "https://research.draconitic.com/paper/352q6feb8vz8t.ris",
  "sources": [
    {
      "first_seen": "2026-11-01T00:20:44Z",
      "native_id": "MED:42954569",
      "source": "europepmc",
      "url": "https://europepmc.org/article/MED/42954569"
    },
    {
      "first_seen": "2026-11-03T12:21:54Z",
      "native_id": "PMC13721176",
      "source": "pmc",
      "url": "https://doi.org/10.1021/jacs.6c11331"
    }
  ],
  "subjects": [
    {
      "field": "chemistry",
      "origin": "journal-openalex:1605|Chemical Reaction Mechanisms",
      "subfield": "organic"
    }
  ],
  "title": "Redox Buffering and Corrosion in Molten Chloride Salts Dictated by Chlorobasicity.",
  "title_text": "Redox Buffering and Corrosion in Molten Chloride Salts Dictated by Chlorobasicity.",
  "type": "peer-reviewed",
  "updated_at": "2026-11-03T12:21:54Z",
  "url": "https://research.draconitic.com/paper/352q6feb8vz8t",
  "venue": "Journal of the American Chemical Society",
  "versions": []
}