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Previously, it is shown that the Mo\u2010nitrogenase could reduce CO<jats:sub>2<\/jats:sub> to CO, but not to hydrocarbons, in an ATP\u2010dependent reaction. Here, it is reported that the ability of the catalytic component of Mo\u2010nitrogenase (MoFe protein) enables ATP\u2010independent reduction of CO<jats:sub>2<\/jats:sub> to up to C<jats:sub>4<\/jats:sub> hydrocarbons in room\u2010temperature reactions driven by a chemical reductant (Eu<jats:sup>II<\/jats:sup>\u2013DTPA) or visible light (via CdS@ZnS (CZS) quantum dots). Moreover, an opposite deuterium isotope effect is observed on the Eu<jats:sup>II<\/jats:sup>\u2013DTPA driven reactions of CO<jats:sub>2<\/jats:sub> reduction by MoFe protein and its V\u2010counterpart (VFe protein), in that the former displays higher activities in H<jats:sub>2<\/jats:sub>O, and the latter displays higher activities in D<jats:sub>2<\/jats:sub>O. These results provide an important foundation for further mechanistic exploration of the nitrogenase\u2010enabled, atypical Fischer\u2013Tropsch type reaction that uses CO<jats:sub>2<\/jats:sub> instead of CO as a substrate; moreover, they serves as a potential template for the future development of nitrogenase\u2010based applications that effectively recycle the greenhouse gas CO<jats:sub>2<\/jats:sub> into valuable fuel products.<\/jats:p>","DOI":"10.1002\/cbic.202500366","type":"journal-article","created":{"date-parts":[[2025,6,16]],"date-time":"2025-06-16T15:21:22Z","timestamp":1750087282000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Reductant\u2010 or Light\u2010Driven ATP\u2010Independent Reduction of CO<sub>2<\/sub> by Nitrogenase MoFe Protein"],"prefix":"10.1002","volume":"26","author":[{"given":"Chi Chung","family":"Lee","sequence":"first","affiliation":[{"name":"Department of Molecular Biology &amp; Biochemistry University of California, Irvine  Irvine CA 92697\u20103900 USA"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-9088-2865","authenticated-orcid":false,"given":"Yilin","family":"Hu","sequence":"additional","affiliation":[{"name":"Department of Molecular Biology &amp; Biochemistry University of California, Irvine  Irvine CA 92697\u20103900 USA"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7366-1526","authenticated-orcid":false,"given":"Markus W.","family":"Ribbe","sequence":"additional","affiliation":[{"name":"Department of Molecular Biology &amp; Biochemistry University of California, Irvine  Irvine CA 92697\u20103900 USA"},{"name":"Department of Chemistry University of California  Irvine CA 92697\u20102025 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