{
  "abstract": "Single-atom catalysts (SACs) are promising enzyme-mimetic active centers, yet mimicking long-range regulation by distal binding pockets in natural metalloenzymes remains challenging. Here, we synthesize conjugated organic SACs bearing tunable peripheral substituents beyond the second coordination sphere (denoted as R-FeSAC; R = F, H, or NH₂) to regulate periodate (PI) activation. F-FeSAC outperforms its H- and NH₂-substituted counterparts because long-range electronic regulation reconfigures the Fe-site microenvironment and strengthens PI adsorption and activation. In situ Raman spectroscopy, galvanic oxidation assays, and electrochemical analyses show that R-FeSAC activates PI to form high-potential metastable intermediates, enabling a direct electron-transfer pathway (ETP) for selective pollutant removal through polymerization, rather than radical or singlet-oxygen pathways. Fluorine substitution reinforces Fe-O interaction with PI and accelerates electron-transfer kinetics through an electron-withdrawing effect. Consistent relationships among pollutant half-wave potentials (φ1/2), LUMO(catalyst/PI)-HOMO(pollutant) energy gaps, and degradation reactivity further support the ETP and indicate that pollutant electron-donating ability governs selectivity. Moreover, an F-functionalized membrane exhibits enhanced durability during continuous-flow operation, while a pilot-scale ETP reactor achieves efficient pollutant degradation in real wastewater without iodate leakage. These findings establish beyond-second-sphere peripheral functionalization as an enzyme-inspired strategy for PI activation and polymerization-mediated water purification.",
  "abstract_shown": true,
  "affiliations": [
    "Zhejiang Key Laboratory of Environment and Health of New Pollutants, School of Environment, Hangzhou Institute for Advanced Study, University of Chinese Academy of Sciences, Hangzhou, 310024, P.R. China.",
    "Zhejiang Key Laboratory of Low-carbon Control Technology for Industrial Pollution, College of Environment, Zhejiang University of Technology, Hangzhou, Zhejiang, 310032, PR China.",
    "State Key Laboratory of Environmental Chemistry and Ecotoxicology, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing, 100085, PR China.",
    "Zhejiang Key Laboratory of Environment and Health of New Pollutants, School of Environment, Hangzhou Institute for Advanced Study, University of Chinese Academy of Sciences, Hangzhou, 310024, P.R. China. zhanghaiyan@ucas.ac.cn.",
    "State Key Laboratory of Hydraulics and Mountain River Engineering, College of Architecture and Environment, Sichuan University, Chengdu, 610065, PR China. laibo@scu.edu.cn.",
    "Zhejiang Key Laboratory of Environment and Health of New Pollutants, School of Environment, Hangzhou Institute for Advanced Study, University of Chinese Academy of Sciences, Hangzhou, 310024, P.R. China. zengtao@ucas.ac.cn.",
    "Zhejiang Key Laboratory of Low-carbon Control Technology for Industrial Pollution, College of Environment, Zhejiang University of Technology, Hangzhou, Zhejiang, 310032, PR China. zengtao@ucas.ac.cn."
  ],
  "article_type": "research support, non u.s. gov't",
  "arxiv": null,
  "author_total": 8,
  "authors": [
    {
      "affs": [
        0,
        1
      ],
      "name": "Sijia Jin"
    },
    {
      "affs": [
        0,
        1
      ],
      "name": "Xiaofeng Tang"
    },
    {
      "affs": [
        1
      ],
      "name": "Zhiqiao He"
    },
    {
      "affs": [
        1
      ],
      "name": "Shuang Song",
      "orcid": "0000-0001-8033-6839"
    },
    {
      "affs": [
        0,
        2
      ],
      "name": "Yaqi Cai",
      "orcid": "0000-0002-2805-5535"
    },
    {
      "affs": [
        3
      ],
      "name": "Haiyan Zhang"
    },
    {
      "affs": [
        4
      ],
      "name": "Bo Lai",
      "orcid": "0000-0002-7105-1345"
    },
    {
      "affs": [
        5,
        6
      ],
      "name": "Tao Zeng",
      "orcid": "0000-0003-1358-5354"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/2net054d3qhcp.bib",
  "cited_by": 0,
  "doi": "10.1038/s41467-026-77805-5",
  "fulltext_url": "https://europepmc.org/articles/PMC13680503",
  "id": "2net054d3qhcp",
  "issns": [
    "2041-1723"
  ],
  "landing_url": "https://europepmc.org/article/MED/42897163",
  "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",
      "2312|Advanced oxidation water treatment"
    ]
  ],
  "openalex": "W7213445089",
  "pdf_url": "https://europepmc.org/articles/PMC13680503?pdf=render",
  "pmcid": "PMC13680503",
  "pmid": "42897163",
  "published": "2026-09-17",
  "publisher": null,
  "ris": "https://research.draconitic.com/paper/2net054d3qhcp.ris",
  "sources": [
    {
      "first_seen": "2026-10-30T12:19:41Z",
      "native_id": "MED:42897163",
      "source": "europepmc",
      "url": "https://europepmc.org/article/MED/42897163"
    }
  ],
  "subjects": [
    {
      "field": "earth",
      "origin": "openalex:2312|Advanced oxidation water treatment",
      "subfield": "hydrology-soils"
    }
  ],
  "title": "Enzyme-mimicking peripheral substituents beyond the second coordination sphere tune single-atom catalysts for periodate activation.",
  "title_text": "Enzyme-mimicking peripheral substituents beyond the second coordination sphere tune single-atom catalysts for periodate activation.",
  "type": "peer-reviewed",
  "updated_at": "2026-10-30T12:19:41Z",
  "url": "https://research.draconitic.com/paper/2net054d3qhcp",
  "venue": "Nature communications",
  "versions": []
}