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The reaction pathways of photocatalytic generation of C\n                    <jats:sub>2,3<\/jats:sub>\n                    paraffin and C\n                    <jats:sub>2<\/jats:sub>\n                    H\n                    <jats:sub>4<\/jats:sub>\n                    from CO\n                    <jats:sub>2<\/jats:sub>\n                    are mostly unclear. Herein, a Co\n                    <jats:sup>0<\/jats:sup>\n                    \u2212ZrO\n                    <jats:sub>2<\/jats:sub>\n                    photocatalyst converted CO\n                    <jats:sub>2<\/jats:sub>\n                    into C\n                    <jats:sub>1\u20133<\/jats:sub>\n                    paraffin, while selectively converting CO into C\n                    <jats:sub>2<\/jats:sub>\n                    H\n                    <jats:sub>4<\/jats:sub>\n                    and C\n                    <jats:sub>3<\/jats:sub>\n                    H\n                    <jats:sub>6<\/jats:sub>\n                    (6.0\u00b10.6\u2005\u03bcmol\u2009h\n                    <jats:sup>\u22121<\/jats:sup>\n                    \u2009g\n                    <jats:sub>cat<\/jats:sub>\n                    <jats:sup>\u22121<\/jats:sup>\n                    , 70\u2005mol\u2009%) only under UV\/Visible light. The photocatalytic cycle was conducted under\n                    <jats:sup>13<\/jats:sup>\n                    CO and H\n                    <jats:sub>2<\/jats:sub>\n                    , with subsequent evacuation and flushing with CO. This iterative process led to an increase in the population of C\n                    <jats:sub>2<\/jats:sub>\n                    H\n                    <jats:sub>4<\/jats:sub>\n                    and C\n                    <jats:sub>3<\/jats:sub>\n                    H\n                    <jats:sub>6<\/jats:sub>\n                    up to 61\u201387\u2005mol\u2009%, attributed to the accumulation of CH\n                    <jats:sub>2<\/jats:sub>\n                    species at the interface between Co\n                    <jats:sup>0<\/jats:sup>\n                    nanoparticles and the ZrO\n                    <jats:sub>2<\/jats:sub>\n                    surface. CO\n                    <jats:sub>2<\/jats:sub>\n                    adsorbed onto the O vacancies of the ZrO\n                    <jats:sub>2<\/jats:sub>\n                    surface, with resulting COH species undergoing hydrogenation on the Co\n                    <jats:sup>0<\/jats:sup>\n                    surface to yield C\n                    <jats:sub>1\u20133<\/jats:sub>\n                    paraffin using either H\n                    <jats:sub>2<\/jats:sub>\n                    or H\n                    <jats:sub>2<\/jats:sub>\n                    O (g, l) as the reductant. In contrast, CO adsorbed on the Co\n                    <jats:sup>0<\/jats:sup>\n                    surface, converted to HCOH species, and then split into CH and OH species at the Co and O vacancy sites on ZrO\n                    <jats:sub>2<\/jats:sub>\n                    , respectively. This comprehensive study elucidates intricate photocatalytic pathways governing the transformation of CO\n                    <jats:sub>2<\/jats:sub>\n                    into paraffin and CO to olefins.\n                  <\/jats:p>","DOI":"10.1002\/anie.202412090","type":"journal-article","created":{"date-parts":[[2024,9,18]],"date-time":"2024-09-18T10:55:01Z","timestamp":1726656901000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":7,"title":["Exchange of CO\n                    <sub>2<\/sub>\n                    with CO as Reactant Switches Selectivity in Photoreduction on Co\u2212ZrO\n                    <sub>2<\/sub>\n                    from C\n                    <sub>1\u20133<\/sub>\n                    Paraffin to Small Olefins"],"prefix":"10.1002","volume":"63","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-4840-8625","authenticated-orcid":false,"given":"Tarik","family":"Loumissi","sequence":"first","affiliation":[{"name":"Department of Chemistry Graduate School of Science Chiba University  Yayoi 1\u201333, Inage-ku Chiba 263-8522 Japan"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-7224-7107","authenticated-orcid":false,"given":"Rento","family":"Ishii","sequence":"additional","affiliation":[{"name":"Department of Chemistry Graduate School of Science Chiba University  Yayoi 1\u201333, Inage-ku Chiba 263-8522 Japan"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5014-9079","authenticated-orcid":false,"given":"Keisuke","family":"Hara","sequence":"additional","affiliation":[{"name":"Department of Chemistry Graduate School of Science Chiba University  Yayoi 1\u201333, Inage-ku Chiba 263-8522 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