{
  "abstract": "While oxide-supported Ni-cluster catalysts are highly active and stable for dry reforming of methane, the size-dependent role of metal-support interactions remains elusive. Here, we deploy a comprehensive framework-integrating density functional theory (DFT), Ab initio molecular dynamics (AIMD), and microkinetic modeling-to elucidate the structure-dynamic-reactivity relationship of six Ni clusters (Ni1 to Ni16) under realistic reaction conditions. DFT reveals that increasing cluster size enhances supportto-metal electron transfer and induces electronic segregation, ultimately driving the formation of robust bifunctional interfacial sites. Furthermore, AIMD simulations indicate that while larger clusters maintain structural rigidity, medium-sized clusters exhibit dynamic fluxionality, reconstructing into highly active, transient single-atom-like configurations at elevated temperatures. Using carbon (EC) and hydrogen (EH) adsorption energies as descriptors, the microkinetic models yield distinct volcano plots for CO and H2 formation revealing a fundamental decoupling in their electronic requirements. Coverage analysis highlights a pronounced size effect: mechanistic shift: small clusters are thermodynamically quenched by oxygen poisoning, whereas large clusters are kinetically bottlenecked by inefficient H-H coupling. Ultimately, the Ni8 configuration achieves an optimal balance between these competing constraints, demonstrating that leveraging dynamic fluxionality and cluster nuclearity offers a powerful strategy to bypass static scaling relations in complex reforming reactions.",
  "abstract_shown": true,
  "affiliations": [
    "Key Laboratory of Precision and Intelligent Chemistry",
    "University of Science and Technology of China",
    "Suzhou Institute for Advanced Research, University of Science and Technology of China",
    "National Institute of Clean-and-Low-Carbon Energy, China Energy Investment Corporation Ltd.",
    "School of Material Science and Engineering",
    "Northeastern University"
  ],
  "article_type": null,
  "arxiv": null,
  "author_total": 9,
  "authors": [
    {
      "name": "Ziyu Mei"
    },
    {
      "affs": [
        0,
        1
      ],
      "name": "Jielin Chen"
    },
    {
      "affs": [
        2
      ],
      "name": "Wenjie Du"
    },
    {
      "affs": [
        3
      ],
      "name": "Quan Lin"
    },
    {
      "affs": [
        4,
        5
      ],
      "name": "Yuping Ren"
    },
    {
      "name": "Yang Wang"
    },
    {
      "name": "Gaowu Qin"
    },
    {
      "name": "Chuangwei Liu",
      "orcid": "0000-0002-8256-6053"
    },
    {
      "affs": [
        0,
        1
      ],
      "name": "Jun Jiang"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/e0djvnag1y0wg.bib",
  "cited_by": 0,
  "doi": "10.26434/chemrxiv.15011095/v1",
  "fulltext_url": null,
  "id": "e0djvnag1y0wg",
  "issns": [],
  "landing_url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15011095/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",
      "1503|Catalysts for Methane Reforming"
    ]
  ],
  "openalex": "W7223804120",
  "pdf_url": "https://chemrxiv.org/doi/pdf/10.26434/chemrxiv.15011095/v1",
  "pmcid": null,
  "pmid": null,
  "published": "2026-10-27",
  "publisher": "American Chemical Society (ACS)",
  "ris": "https://research.draconitic.com/paper/e0djvnag1y0wg.ris",
  "sources": [
    {
      "first_seen": "2026-10-30T12:17:26Z",
      "native_id": "10.26434/chemrxiv.15011095",
      "source": "chemrxiv",
      "url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15011095/v1"
    }
  ],
  "subjects": [
    {
      "field": "chemistry",
      "origin": "openalex:1503|Catalysts for Methane Reforming",
      "subfield": "catalysis"
    }
  ],
  "title": "Dynamic Fluxionality of Nickel Clusters Bypasses Linear Scaling Relations in Methane Dry Reforming",
  "title_text": "Dynamic Fluxionality of Nickel Clusters Bypasses Linear Scaling Relations in Methane Dry Reforming",
  "type": "preprint",
  "updated_at": "2026-10-30T12:17:26Z",
  "url": "https://research.draconitic.com/paper/e0djvnag1y0wg",
  "venue": "ChemRxiv",
  "versions": []
}