{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,7,31]],"date-time":"2026-07-31T14:09:02Z","timestamp":1785506942104,"version":"3.56.0"},"reference-count":44,"publisher":"American Chemical Society (ACS)","issue":"29","license":[{"start":{"date-parts":[[2026,7,16]],"date-time":"2026-07-16T00:00:00Z","timestamp":1784160000000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/100006151","name":"Basic Energy Sciences","doi-asserted-by":"publisher","award":["DE-SC0020983"],"award-info":[{"award-number":["DE-SC0020983"]}],"id":[{"id":"10.13039\/100006151","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":[],"published-print":{"date-parts":[[2026,7,29]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>Molecules derived from lignocellulosic biomass are oxygenates with multiple oxygen-containing functional groups, such as hydroxyl and carbonyl groups. Therefore, the ability to selectively reduce a specific oxygenate group is essential for the reductive upgrading of such molecules. Previous studies on electrochemical biomass conversion have shown that alcohol hydrogenolysis, which involves cleavage of the \u03c3(C\u2013Oalcohol) bond, is extremely challenging for furfural and 5-hydroxymethylfurfural (HMF) derivatives, including furfuryl alcohol, 5-methylfurfuryl alcohol (MFA), and 2,5-bis(hydroxymethyl)furan (BHMF). In contrast, HMF itself undergoes alcohol hydrogenolysis relatively easily in acidic aqueous media. Considering that the only structural difference between HMF and BHMF or MFA is the presence of a carbonyl group, this observation raises the question of whether the carbonyl group in HMF facilitates alcohol hydrogenolysis. In this study, we designed systematic experiments to provide a coherent explanation of when and how a carbonyl group enables hydrogenolysis of a copresent alcohol group. Specifically, we show that alcohol hydrogenolysis in HMF proceeds via reduction of the carbonyl group to a ketyl radical, followed by a spin-center shift (SCS) through extended \u03c0 conjugation. We also elucidate the effect of pH on the selectivity between carbonyl hydrogenation and alcohol hydrogenolysis, both of which share the ketyl radical intermediate. This mechanistic understanding enhances our ability to predict and control alcohol hydrogenolysis in the reductive upgrading of biomass-derived oxygenates.<\/jats:p>","DOI":"10.1021\/jacs.6c09300","type":"journal-article","created":{"date-parts":[[2026,7,16]],"date-time":"2026-07-16T21:14:21Z","timestamp":1784236461000},"page":"31393-31404","source":"Crossref","is-referenced-by-count":0,"title":["Understanding Electrochemical\nAlcohol Hydrogenolysis\nEnabled by Carbonyl Reduction in Lignocellulosic Biomass-Derived Aromatic\nOxygenates"],"prefix":"10.1021","volume":"148","author":[{"given":"Myohwa","family":"Ko","sequence":"first","affiliation":[{"name":"University of Wisconsin-Madison , , , ,","place":["Madison, Wisconsin, United States, 53706"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Xin","family":"Yuan","sequence":"additional","affiliation":[{"name":"University of Wisconsin-Madison , , , ,","place":["Madison, Wisconsin, United States, 53706"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-1750-5219","authenticated-orcid":true,"given":"Kwanpyung","family":"Lee","sequence":"additional","affiliation":[{"name":"University of Wisconsin-Madison , , , ,","place":["Madison, Wisconsin, United States, 53706"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-1438-117X","authenticated-orcid":true,"given":"J. R.","family":"Schmidt","sequence":"additional","affiliation":[{"name":"University of Wisconsin-Madison , , , ,","place":["Madison, Wisconsin, United States, 53706"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-1945-8794","authenticated-orcid":true,"given":"Kyoung-Shin","family":"Choi","sequence":"additional","affiliation":[{"name":"University of Wisconsin-Madison , , , ,","place":["Madison, Wisconsin, United States, 53706"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,7,16]]},"reference":[{"issue":"5760","key":"2026073109213062600_cit1","doi-asserted-by":"publisher","first-page":"484","DOI":"10.1126\/science.1114736","article-title":"The Path Forward\nfor Biofuels and Biomaterials","volume":"311","author":"Ragauskas","year":"2006","journal-title":"Science"},{"issue":"1","key":"2026073109213062600_cit2","doi-asserted-by":"publisher","DOI":"10.1038\/s41467-025-56472-y","article-title":"Advances in Lignocellulosic\nFeedstocks for Bioenergy and Bioproducts","volume":"16","author":"Sulis","year":"2025","journal-title":"Nat.\nCommun."},{"issue":"4","key":"2026073109213062600_cit3","doi-asserted-by":"publisher","first-page":"339","DOI":"10.3390\/agriculture2040339","article-title":"The Agricultural\nEthics of Biofuels: The Food vs. Fuel Debate","volume":"2","author":"Thompson","year":"2012","journal-title":"Agriculture"},{"key":"2026073109213062600_cit4","doi-asserted-by":"publisher","DOI":"10.1016\/j.rser.2022.112393","article-title":"Advancements\nin Net-Zero Pertinency\nof Lignocellulosic Biomass for Climate Neutral Energy Production","volume":"161","author":"Nahak","year":"2022","journal-title":"Renewable Sustainable Energy Rev."},{"key":"2026073109213062600_cit5","doi-asserted-by":"publisher","DOI":"10.1016\/j.chemosphere.2021.131824","article-title":"Lignocellulosic Biomass-Based\nPyrolysis: A Comprehensive Review","volume":"286","author":"K N","year":"2022","journal-title":"Chemosphere"},{"issue":"7","key":"2026073109213062600_cit6","doi-asserted-by":"publisher","DOI":"10.3390\/pr8070799","article-title":"Recent Insights into\nLignocellulosic Biomass Pyrolysis: A Critical Review on Pretreatment,\nCharacterization, and Products Upgrading","volume":"8","author":"Zadeh","year":"2020","journal-title":"Processes"},{"key":"2026073109213062600_cit7","doi-asserted-by":"publisher","DOI":"10.1016\/j.cogsc.2023.100803","article-title":"Lignocellulosic\nBiomass Conversion into 5-Hydroxymethylfurfural\nand 2,5-Dimethylfuran, and Role of the \u2018Green\u2019 Solvent","volume":"41","author":"Lim","year":"2023","journal-title":"Curr. 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