{
  "abstract": "The restructuring of a catalyst’s interface with its support can be tailored via strong metal-support interactions (SMSI) in order to achieve desired product selectivity. SMSI is usually associated with reductive conditions, where a reduced oxide support covers a supported metal phase and alters catalytic activity. Here, pretreatment-dependent SMSI of rhodium nanoparticles supported on rutile titania is shown to control the selectivity profile for CO 2 hydrogenation reactions between methanation and the reverse water-gas shift reaction at 500 °C. Oxidative pretreatments at 400 °C were found to promote methanation with an initial rate of 5.1 mol/mol Rh /s for an O 2 pretreated sample and 5.8 mol/mol Rh /s for an O 2 followed by H 2 pretreated sample, whereas a H 2 pretreatment at 400 °C suppressed the methanation reaction to an initial rate of 0.25 mol/mol Rh /s. Instead of following classical methods of catalyst restructuring, such as sintering and reductive SMSI, the catalyst forms an SMSI overlayer under oxidative conditions, which restructures its active sites to selectively promote the methanation reaction. The effects of the restructuring are long-lived and dominated the catalyst selectivity even after more than 100 hours under reaction conditions. We demonstrate that this oxidative SMSI overlayer grows via a rhodium titanate intermediate and is necessary for creating active sites for methanation, shifting the catalyst’s selectivity away from the RWGS reaction. Theoretical calculations further demonstrate the thermodynamic favorability of TiO 2 overlayer growth under experimentally-relevant oxidative conditions. These results demonstrate that catalyst pretreatment conditions are a facile and effective tool for tuning the catalyst-support interface by allowing for the construction of an oxidative strong metal-support interaction that determines the product selectivity of supported rhodium catalysts.",
  "abstract_shown": true,
  "affiliations": [
    "Department of Chemical Engineering",
    "Stanford University",
    "Department of Chemistry and Biochemistry",
    "University of California",
    "Stanford Synchrotron Radiation Lightsource",
    "SLAC National Accelerator Laboratory",
    "Center for Functional Nanomaterials",
    "Brookhaven National Laboratory",
    "Pennsylvania State University",
    "Department of Chemistry",
    "Department of Chemical and Petroleum Engineering, Physics",
    "University of Pittsburgh",
    "SUNCAT Center for Interface Science and Catalysis",
    "CO2 Research Center (CORC",
    "Aarhus University"
  ],
  "article_type": null,
  "arxiv": null,
  "author_total": 16,
  "authors": [
    {
      "affs": [
        0,
        1
      ],
      "name": "Jake Heinlein",
      "orcid": "0000-0001-6225-7504"
    },
    {
      "affs": [
        2,
        3
      ],
      "name": "Jake Erbez"
    },
    {
      "affs": [
        4,
        5
      ],
      "name": "Anastassiya Khan"
    },
    {
      "affs": [
        6,
        7
      ],
      "name": "Sabrina M. Gericke"
    },
    {
      "affs": [
        6,
        7
      ],
      "name": "Xiaobo Chen"
    },
    {
      "affs": [
        6,
        7
      ],
      "name": "Meng Li"
    },
    {
      "affs": [
        0,
        8
      ],
      "name": "Greg Barber"
    },
    {
      "affs": [
        4,
        5
      ],
      "name": "Zhihengyu Chen"
    },
    {
      "affs": [
        5
      ],
      "name": "Christopher J. Tassone"
    },
    {
      "affs": [
        0,
        8,
        9
      ],
      "name": "Robert M. Rioux"
    },
    {
      "affs": [
        6,
        7
      ],
      "name": "Ashley R. Head"
    },
    {
      "affs": [
        6,
        7,
        10,
        11
      ],
      "name": "Judith Yang"
    },
    {
      "affs": [
        4,
        5,
        12,
        1
      ],
      "name": "Adam S. Hoffman"
    },
    {
      "affs": [
        4,
        5,
        12,
        1
      ],
      "name": "Simon R. Bare"
    },
    {
      "affs": [
        2,
        3
      ],
      "name": "Anastassia N. Alexandrova"
    },
    {
      "affs": [
        0,
        1,
        12,
        13,
        14
      ],
      "name": "Matteo Cargnello"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/1sfkvpsmp5e3j.bib",
  "cited_by": 0,
  "doi": "10.26434/chemrxiv.15009725/v1",
  "fulltext_url": null,
  "id": "1sfkvpsmp5e3j",
  "issns": [],
  "landing_url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009725/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": "W7215085698",
  "pdf_url": "https://chemrxiv.org/doi/pdf/10.26434/chemrxiv.15009725/v1",
  "pmcid": null,
  "pmid": null,
  "published": "2026-10-01",
  "publisher": "American Chemical Society (ACS)",
  "ris": "https://research.draconitic.com/paper/1sfkvpsmp5e3j.ris",
  "sources": [
    {
      "first_seen": "2026-10-30T12:17:21Z",
      "native_id": "10.26434/chemrxiv.15009725",
      "source": "chemrxiv",
      "url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009725/v1"
    }
  ],
  "subjects": [
    {
      "field": "chemistry",
      "origin": "openalex:1503|Catalysts for Methane Reforming",
      "subfield": "catalysis"
    }
  ],
  "title": "Oxidative strong metal-support interaction determines selectivity in supported Rh catalysts for CO2 hydrogenation",
  "title_text": "Oxidative strong metal-support interaction determines selectivity in supported Rh catalysts for CO2 hydrogenation",
  "type": "preprint",
  "updated_at": "2026-10-30T12:17:21Z",
  "url": "https://research.draconitic.com/paper/1sfkvpsmp5e3j",
  "venue": "ChemRxiv",
  "versions": []
}