{
  "abstract": "Electrochemical conversion of CO2 into formate (HCOO−) represents a promising strategy for mitigating global warming while producing an industrially important chemical. Polyoxometalates (POMs), anionic molecular metal‐oxo clusters, offer unique opportunities as catalysts and catalyst precursors for the electrochemical CO2 reduction reaction (CO2RR) owing to their structural diversity, compositional tunability, and flexibility in countercation selection. Despite these advantages, effective strategies for developing POM‐based CO2RR catalysts with high selectivity toward HCOO− remain limited. In this study, we demonstrate countercation manipulation as a powerful approach to achieving selective HCOO− production using a bismuth (Bi)‐incorporated POM, [Bi4O(γ‐SiW10O36)2(OAc)]7− (Bi4). Under gas‐diffusion CO2RR conditions with a 2 M KHCO3 aqueous electrolyte, the Ba2+ salt of Bi4 immobilized on carbon (Ba‐Bi4/C) exhibited high HCOO− selectivity with a Faradaic efficiency of 84.3% at −0.79 VRHE, whereas the corresponding tetra‐n‐butylammonium (TBA+) salt (TBA‐Bi4/C) exhibited substantially lower selectivity (26.6% at −0.79 VRHE). Post‐reaction analyses revealed that both catalysts transformed into highly dispersed Bi species protected by WO x nanoaggregates. Control experiments and detailed characterizations indicated that the countercations, in conjunction with the POM‐derived catalyst structure, play a crucial role in governing CO2RR performance.",
  "abstract_shown": true,
  "affiliations": [
    "Department of Applied Chemistry School of Engineering The University of Tokyo Tokyo Japan",
    "Department of Advanced Materials Science Graduate School of Frontier Sciences The University of Tokyo Kashiwa‐shi Chiba Japan",
    "Department of Chemistry Graduate School of Science Tokyo Metropolitan University Tokyo Japan",
    "Japan Synchrotron Radiation Research Institute (JASRI) Hyogo Japan",
    "Department of Applied Chemistry for Environment Graduate School of Urban Environmental Sciences Tokyo Metropolitan University Tokyo Japan",
    "RIKEN SPring‐8 Center Hyogo Japan",
    "Center for Basic Research on Materials National Institute for Materials Science (NIMS) Tsukuba‐shi Ibaraki Japan",
    "Research Center for Autonomous Systems Materialogy (ASMat) Institute of Integrated Research Institute of Science Tokyo Yokohama‐shi Kanagawa Japan"
  ],
  "article_type": "research article",
  "arxiv": null,
  "author_total": 13,
  "authors": [
    {
      "affs": [
        0
      ],
      "name": "Kimitake Kawakami"
    },
    {
      "affs": [
        0,
        1
      ],
      "name": "Kentaro Yonesato",
      "orcid": "0000-0001-9143-6691"
    },
    {
      "affs": [
        0
      ],
      "name": "Shimon Akino"
    },
    {
      "affs": [
        2
      ],
      "name": "Soichi Kikkawa",
      "orcid": "0000-0002-8193-6374"
    },
    {
      "affs": [
        2
      ],
      "name": "Seiji Yamazoe",
      "orcid": "0000-0002-8382-8078"
    },
    {
      "affs": [
        3
      ],
      "name": "Takuma Kaneko"
    },
    {
      "affs": [
        3
      ],
      "name": "Tomoya Uruga"
    },
    {
      "affs": [
        4
      ],
      "name": "Fumiaki Amano",
      "orcid": "0000-0003-2812-5799"
    },
    {
      "affs": [
        5
      ],
      "name": "Yoshiaki Honjo"
    },
    {
      "affs": [
        5
      ],
      "name": "Takaki Hatsui"
    },
    {
      "affs": [
        6,
        7
      ],
      "name": "Koji Harano",
      "orcid": "0000-0001-6800-8023"
    },
    {
      "affs": [
        0
      ],
      "name": "Kazuya Yamaguchi",
      "orcid": "0000-0002-7661-4936"
    },
    {
      "affs": [
        0,
        1
      ],
      "name": "Kosuke Suzuki",
      "orcid": "0000-0002-8123-1462"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/c8r549mazcvfb.bib",
  "cited_by": 0,
  "doi": "10.1002/chem.71437",
  "fulltext_url": "https://pmc.ncbi.nlm.nih.gov/articles/PMC13716004/",
  "id": "c8r549mazcvfb",
  "issns": [
    "0947-6539",
    "1521-3765"
  ],
  "landing_url": "https://doi.org/10.1002/chem.71437",
  "language": "en",
  "licence": "CC-BY-4.0",
  "licence_label": "CC BY 4.0",
  "licence_source": "article",
  "licence_url": "https://creativecommons.org/licenses/by/4.0/",
  "metadata_licence": null,
  "native_subjects": [
    [
      "heading",
      "Research Article"
    ],
    [
      "openalex",
      "2105|CO2 Reduction Techniques and Catalysts"
    ]
  ],
  "openalex": "W7170048037",
  "pdf_url": null,
  "pmcid": "PMC13716004",
  "pmid": "42485582",
  "published": "2026-07-22",
  "publisher": null,
  "ris": "https://research.draconitic.com/paper/c8r549mazcvfb.ris",
  "sources": [
    {
      "first_seen": "2026-11-01T12:23:10Z",
      "native_id": "PMC13716004",
      "source": "pmc",
      "url": "https://doi.org/10.1002/chem.71437"
    }
  ],
  "subjects": [
    {
      "field": "chemistry",
      "origin": "journal-openalex:1605|Supramolecular Chemistry and Complexes",
      "subfield": "organic"
    }
  ],
  "title": "Countercation Manipulation Enables Selective Electrochemical CO2‐to‐Formate Conversion Over Bi‐Polyoxometalate‐Derived Catalysts",
  "title_text": "Countercation Manipulation Enables Selective Electrochemical CO2‐to‐Formate Conversion Over Bi‐Polyoxometalate‐Derived Catalysts",
  "type": "peer-reviewed",
  "updated_at": "2026-11-01T12:23:10Z",
  "url": "https://research.draconitic.com/paper/c8r549mazcvfb",
  "venue": "Chemistry (Weinheim an Der Bergstrasse, Germany)",
  "versions": []
}