{
  "abstract": "Higher alcohol synthesis from syngas on Rh involves a highly branched and reversible reaction network in which formation of a C–C bond does not necessarily result in productive higher-alcohol synthesis. Here, a thermodynamically consistent first-principles mean-field microkinetic model is constructed to determine how carbon is partitioned among methane, methanol, ethanol, and highercarbon intermediates under steady-state conditions. Across a 100-point temperature–pressure domain, the model exhibits a pronounced activity–selectivity trade-off: conditions that increase turnover progressively favor methane and methanol over ethanol. Reaction-flux analysis reveals that CO insertion provides the dominant entry into the C 2 carbonyl manifold, but 79–94% of this carbonyl flux is recycled toward the C 1 pool across representative kinetic regimes rather than converted productively to ethanol. Consequently, the elementary C–C coupling reactions carry substantial flux while exhibiting relatively small degrees of rate control. Instead, downstream ethoxy hydrogenation becomes increasingly rate controlling, while methane formation and oxygen-removal chemistry strongly influence ethanol productivity. CHO insertion, despite its favorable intrinsic forward barrier, changes from a productive C–C-forming pathway at low activity to a net recycling pathway at high activity, demonstrating that isolated activation barriers do not determine steady-state pathway utilization. Methanol additionally constitutes a major competing sink for oxygenated C 1 carbon. These results show that improving Rh-based higheralcohol synthesis requires not only promoting C–C coupling but also suppressing carbonyl recycling and kinetically trapping C 2 intermediates along the productive ethanol pathway.",
  "abstract_shown": true,
  "affiliations": [
    "School of Innovation and Sustainability",
    "De La Salle University",
    "Center for Quantum Information and Quantum Biology, University of Osaka, 1–2 Machikaneyama-cho, Toyonaka, Osaka, Japan, 560-0043"
  ],
  "article_type": null,
  "arxiv": null,
  "author_total": 2,
  "authors": [
    {
      "affs": [
        0,
        1
      ],
      "name": "Ryan Lacdao Arevalo"
    },
    {
      "affs": [
        2
      ],
      "name": "Hiroshi Nakanishi"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/d3n91q9pnf0qq.bib",
  "cited_by": 0,
  "doi": "10.26434/chemrxiv.15008804/v1",
  "fulltext_url": null,
  "id": "d3n91q9pnf0qq",
  "issns": [],
  "landing_url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008804/v1",
  "language": null,
  "licence": "CC-BY-NC-ND",
  "licence_label": "CC BY-NC-ND",
  "licence_source": "journal",
  "licence_url": "https://creativecommons.org/licenses/by-nc-nd/4.0/",
  "metadata_licence": null,
  "native_subjects": [
    [
      "openalex",
      "1503|Catalysts for Methane Reforming"
    ]
  ],
  "openalex": "W7213263534",
  "pdf_url": "https://chemrxiv.org/doi/pdf/10.26434/chemrxiv.15008804/v1",
  "pmcid": null,
  "pmid": null,
  "published": "2026-09-14",
  "publisher": "American Chemical Society (ACS)",
  "ris": "https://research.draconitic.com/paper/d3n91q9pnf0qq.ris",
  "sources": [
    {
      "first_seen": "2026-10-30T12:17:19Z",
      "native_id": "10.26434/chemrxiv.15008804",
      "source": "chemrxiv",
      "url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008804/v2"
    }
  ],
  "subjects": [
    {
      "field": "chemistry",
      "origin": "openalex:1503|Catalysts for Methane Reforming",
      "subfield": "catalysis"
    }
  ],
  "title": "Carbonyl Recycling Limits Productive Ethanol Formation during Syngas Conversion on Rh(211): A First-Principles Microkinetic Analysis",
  "title_text": "Carbonyl Recycling Limits Productive Ethanol Formation during Syngas Conversion on Rh(211): A First-Principles Microkinetic Analysis",
  "type": "preprint",
  "updated_at": "2026-10-30T12:17:26Z",
  "url": "https://research.draconitic.com/paper/d3n91q9pnf0qq",
  "venue": "ChemRxiv",
  "versions": []
}