{
  "abstract": "Zirconium-based metal-organic frameworks have emerged as promising materials for the capture and detoxification of chemical warfare agents, but the molecular mechanism by which a hierarchical MOF differentiates a hydrophobic reactant from its oxidized product remains incompletely understood. Here, we use molecular dynamics simulations, grand-canonical Monte Carlo adsorption calculations, and periodic density functional theory to examine the dual-hosting behavior of NU-1000 toward sulfur mustard (HD) and mustard sulfoxide (HDO). Rather than treating NU-1000 only as an adsorbent or oxidation catalyst, we resolve how its internal micropore, mesopore, and c-pore interfaces impose distinct confinement environments on reactant and product species. Density functional theory (DFT) calculations show that HD binds most favorably in the c-pore region, with a binding energy of approximately -12.5 kcal/mol, and similarly favorable stabilization in confined micropore environments, whereas substantially weaker binding is observed in the mesopore. Molecular dynamics simulations also reveal sharply different pore residence patterns: HD localizes predominantly in micropores, occupying this region for ∼80% of the trajectory, while HDO samples larger pore environments more broadly, with ∼45% mesopore and ∼34% c-pore occupancy. This pore-selective behavior persists under mixed HD/HDO coadsorption conditions, demonstrating that reactant-product differentiation is intrinsic to the NU-1000 pore network rather than an artifact of isolated single-component simulations. Radial distribution functions further show that HD is stabilized by dispersion-dominated confinement and weak halogen-hydrogen contacts, whereas HDO is governed by more localized, orientation-dependent interactions with hydrated zirconium node sites. These interaction differences produce a pronounced transport asymmetry, with HDO exhibiting a self-diffusion coefficient of 10.6 ± 2.11 × 10-10 m2/s compared with 0.5 ± 0.09 × 10-10 m2/s for HD at comparable loading. The results identify NU-1000 as a dual-function molecular host that couples reactant retention with product mobility, providing an interface-level mechanism relevant to selective CWA detoxification and confined transport in hierarchical porous catalysts.",
  "abstract_shown": true,
  "affiliations": [
    "School of Sustainable Chemical, Biological and Materials Engineering, University of Oklahoma, Norman, Oklahoma73019, United States.",
    "Materials Science and Engineering Program, University of Oklahoma, Norman, Oklahoma73019, United States."
  ],
  "article_type": "research article",
  "arxiv": null,
  "author_total": 2,
  "authors": [
    {
      "affs": [
        0
      ],
      "name": "Farrah S McCormick"
    },
    {
      "affs": [
        0,
        1
      ],
      "name": "Liangliang Huang",
      "orcid": "0000-0003-2358-9375"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/ahwc7x2ypgmta.bib",
  "cited_by": 0,
  "doi": "10.1021/acs.langmuir.6c04057",
  "fulltext_url": "https://europepmc.org/articles/PMC13689922",
  "id": "ahwc7x2ypgmta",
  "issns": [
    "0743-7463",
    "1520-5827"
  ],
  "landing_url": "https://europepmc.org/article/MED/42899887",
  "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": [
    [
      "openalex",
      "1604|Metal-Organic Frameworks: Synthesis and Applications"
    ]
  ],
  "openalex": "W7221307847",
  "pdf_url": "https://europepmc.org/articles/PMC13689922?pdf=render",
  "pmcid": "PMC13689922",
  "pmid": "42899887",
  "published": "2026-10-01",
  "publisher": null,
  "ris": "https://research.draconitic.com/paper/ahwc7x2ypgmta.ris",
  "sources": [
    {
      "first_seen": "2026-10-30T12:19:37Z",
      "native_id": "MED:42899887",
      "source": "europepmc",
      "url": "https://europepmc.org/article/MED/42899887"
    }
  ],
  "subjects": [
    {
      "field": "chemistry",
      "origin": "openalex:1604|Metal-Organic Frameworks: Synthesis and Applications",
      "subfield": "inorganic"
    }
  ],
  "title": "Interfacial Confinement Enables Dual Hosting of Sulfur Mustard and Mustard Sulfoxide in NU-1000.",
  "title_text": "Interfacial Confinement Enables Dual Hosting of Sulfur Mustard and Mustard Sulfoxide in NU-1000.",
  "type": "peer-reviewed",
  "updated_at": "2026-10-30T12:19:37Z",
  "url": "https://research.draconitic.com/paper/ahwc7x2ypgmta",
  "venue": "Langmuir : the ACS journal of surfaces and colloids",
  "versions": []
}