{
  "abstract": "Electrochemical nitrate reduction reaction (eNO3-RR) offers a promising route for sustainable ammonia production while mitigating nitrate pollution. Yet high NH3 selectivity remains challenging owing to proton-coupled multi-electron transfer pathways and competing hydrogen evolution reaction (HER). Herein, we report a trinuclear Cu nanocluster-based covalent organic framework (CuMePh) featuring methylfunctionalized π-conjugated extended porous framework that provides a molecular-level strategy for modifying the interfacial wettability and electronic environment of the catalytic framework. Benefiting from this modulation strategy, CuMePh exhibits a maximum faradaic efficiency (FE) of 98% for nitrate to ammonia conversion, with an NH3 production rate of 2161 μg h-1 cm-2 (5402.5 μg h-1 mg-1 cat.) at -0.5 V versus RHE under the investigated alkaline conditions. Compared with the non-methylated CuPh analogue, CuMePh also exhibits a higher water contact angle. Density functional theory (DFT) calculations reveal that the electronenriched Cu3-cluster nodes in CuMePh facilitate nitrate activation and sequential hydrogenation by lowering the free-energy requirement and optimizing intermediates binding, while simultaneously suppressing the competing HER. This work highlights a molecular-level design principle that couples electronic-structure engineering with interfacial-property regulation in nanocluster-based COFs, offering new opportunities for developing highly selective electrocatalysts for sustainable nitrogen-cycle transformations.",
  "abstract_shown": true,
  "affiliations": [],
  "article_type": null,
  "arxiv": null,
  "author_total": 12,
  "authors": [
    {
      "name": "Sriyanka Bhandari"
    },
    {
      "name": "Somnath Paitandi"
    },
    {
      "name": "Rohit Sankapal"
    },
    {
      "name": "Jumana Ishrat"
    },
    {
      "name": "Imran Hussain"
    },
    {
      "name": "Sabuj Kanti Das"
    },
    {
      "name": "Sujan Mondal"
    },
    {
      "name": "Riki Nakatani"
    },
    {
      "name": "Tokuhisa Kawawaki"
    },
    {
      "name": "Kalishankar Bhattacharyya"
    },
    {
      "name": "Cafer T. Yavuz"
    },
    {
      "name": "Yuichi Negishi",
      "orcid": "0000-0003-3965-1399"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/586w010f5a2zn.bib",
  "cited_by": 0,
  "doi": "10.26434/chemrxiv.15010880/v1",
  "fulltext_url": null,
  "id": "586w010f5a2zn",
  "issns": [],
  "landing_url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010880/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|Ammonia Synthesis and Nitrogen Reduction"
    ]
  ],
  "openalex": "W7223184572",
  "pdf_url": "https://chemrxiv.org/doi/pdf/10.26434/chemrxiv.15010880/v1",
  "pmcid": null,
  "pmid": null,
  "published": "2026-10-22",
  "publisher": "American Chemical Society (ACS)",
  "ris": "https://research.draconitic.com/paper/586w010f5a2zn.ris",
  "sources": [
    {
      "first_seen": "2026-10-30T12:17:26Z",
      "native_id": "10.26434/chemrxiv.15010880",
      "source": "chemrxiv",
      "url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010880/v1"
    }
  ],
  "subjects": [
    {
      "field": "chemistry",
      "origin": "openalex:1503|Ammonia Synthesis and Nitrogen Reduction",
      "subfield": "catalysis"
    }
  ],
  "title": "Methyl-Induced Hydrophobicity and Electronically Tuned Copper Nanocluster COF for Highly Selective Nitrate to Ammonia Electrosynthesis",
  "title_text": "Methyl-Induced Hydrophobicity and Electronically Tuned Copper Nanocluster COF for Highly Selective Nitrate to Ammonia Electrosynthesis",
  "type": "preprint",
  "updated_at": "2026-10-30T12:17:26Z",
  "url": "https://research.draconitic.com/paper/586w010f5a2zn",
  "venue": "ChemRxiv",
  "versions": []
}