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Herein, we probe the activation of CO\n                    <jats:sub>2<\/jats:sub>\n                    on highly defective TiO\n                    <jats:sub>2<\/jats:sub>\n                    in situ using synchrotron\u2010based near\u2010ambient pressure X\u2010ray photoelectron spectroscopy between 0.1 mbar and 2.6 mbar from room temperature to 700 K. Multiple carbon surface intermediates form upon CO\n                    <jats:sub>2<\/jats:sub>\n                    activation. The presence of key intermediates acts as a fingerprint for the population of different reaction pathways, that is, promotion or suppression of selected reaction steps in various gas environments. In the absence of potent H\/OH donors, the formyl, glyoxal, formaldehyde and carbene pathways are populated simultaneously. However, aqueous atmospheres boost intermediate formation and promote oxygen\u2010rich organic molecules, suppressing coke formation along the carbene pathway. Thermal loss of hydroxyls above \u2248550 K triggers the population of such oxygen\u2010lean routes, along with a decrease in carbon intermediates, converging to the chemistry under water\u2010free conditions. Our results highlight reduced titania as a noble metal\u2010free CO\n                    <jats:sub>2<\/jats:sub>\n                    activation catalyst and demonstrate how water can be used to favor the desired product distribution. The findings herein will guide the development of sustainable catalysts from heavily reduced oxides, for example, black titania, for platform chemicals based on CO\n                    <jats:sub>2<\/jats:sub>\n                    as a building block.\n                  <\/jats:p>","DOI":"10.1002\/anie.7574479","type":"journal-article","created":{"date-parts":[[2026,5,13]],"date-time":"2026-05-13T14:50:26Z","timestamp":1778683826000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Role of Water in Low\u2010Temperature CO\n                    <sub>2<\/sub>\n                    Reduction at Defect\u2010Rich TiO\n                    <sub>2<\/sub>"],"prefix":"10.1002","volume":"65","author":[{"given":"Justin","family":"Klimek","sequence":"first","affiliation":[{"name":"Institute of Chemistry Carl von Ossietzky University of Oldenburg  Oldenburg Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Filip","family":"Hallb\u00f6\u00f6k","sequence":"additional","affiliation":[{"name":"Department of Process and Life Science Engineering Lund University  Lund Sweden"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Niko","family":"Kruse","sequence":"additional","affiliation":[{"name":"Institute of Chemistry Carl von Ossietzky University of Oldenburg  Oldenburg Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Fangliang","family":"Li","sequence":"additional","affiliation":[{"name":"Institute of Chemistry Carl von Ossietzky University of Oldenburg  Oldenburg Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Sara","family":"Blomberg","sequence":"additional","affiliation":[{"name":"Department of Process and Life Science Engineering Lund University  Lund 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