{
  "abstract": "Biomass is the only viable source of renewable terrestrial carbon. Lignin, a rigid structure of biomass, has been investigated for its difficulty to depolymerize. β-O-4 linkages, which account for 50-60% of all inter-unit bonds, are the primary targets for breaking down the polymer to derive aromatic compounds. Although transition-metal-assisted oxidative cleavage has been identified as a promising method, the conventionally used 4d and 5d transition metals are scarce and expensive, limiting industrial scalability. This study evaluates the efficiency of cost-effective and earth-abundant transition metals Cu(II), Mn(II), Ti(II), and V(II) for the oxidative cleavage of the β-O-4 bond. Using the hybrid density functional B3LYP and wave function CCSD (T) functionals, geometry optimizations for the adducts, transition states, and intermediate complexes were conducted on methoxyethane as a simplified model dimer. Our results identify vanadium as the most promising catalyst kinetically, with a Boltzmann population of ~100%, and copper as the most promising catalyst thermodynamically, with a Boltzmann population of 99.69%. Additional verification using the actual β-O-4 model compound, guaiacylglycerol-β-guaiacyl ether, showed that both V and Cu stretched the target bond to >2.5 Å, exceeding the C–O bond dissociation threshold (1.7–1.8 Å). Given their strong performance as homogeneous catalysts, vanadium and copper show promise for incorporation into heterogeneous catalyst architectures to enable industrial-scale biomass conversion for applications in sustainable materials and biofuels.",
  "abstract_shown": true,
  "affiliations": [
    "Independent Researcher",
    "Department of Chemistry",
    "Stanford Online High School"
  ],
  "article_type": null,
  "arxiv": null,
  "author_total": 2,
  "authors": [
    {
      "affs": [
        0
      ],
      "name": "Ellie Shen",
      "orcid": "0009-0003-1535-5971"
    },
    {
      "affs": [
        1,
        2
      ],
      "name": "Nick DeMello"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/ccqma93xeee5k.bib",
  "cited_by": 0,
  "doi": "10.26434/chemrxiv.15008291/v1",
  "fulltext_url": null,
  "id": "ccqma93xeee5k",
  "issns": [],
  "landing_url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008291/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",
      "2204|Lignin and Wood Chemistry"
    ]
  ],
  "openalex": "W7208713274",
  "pdf_url": "https://chemrxiv.org/doi/pdf/10.26434/chemrxiv.15008291/v1",
  "pmcid": null,
  "pmid": null,
  "published": "2026-09-04",
  "publisher": "American Chemical Society (ACS)",
  "ris": "https://research.draconitic.com/paper/ccqma93xeee5k.ris",
  "sources": [
    {
      "first_seen": "2026-10-30T12:17:17Z",
      "native_id": "10.26434/chemrxiv.15008291",
      "source": "chemrxiv",
      "url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008291/v1"
    }
  ],
  "subjects": [
    {
      "field": "chemistry",
      "origin": "source:chemrxiv",
      "subfield": "general"
    }
  ],
  "title": "A DFT Study of Oxidative Lignin β-O-4 Bond Cleavage by Transition-Metal Catalysis",
  "title_text": "A DFT Study of Oxidative Lignin β-O-4 Bond Cleavage by Transition-Metal Catalysis",
  "type": "preprint",
  "updated_at": "2026-10-30T12:17:17Z",
  "url": "https://research.draconitic.com/paper/ccqma93xeee5k",
  "venue": "ChemRxiv",
  "versions": []
}