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However, achieving high selectivity at industrially relevant current densities remains challenging due to inefficient *CO utilization and strong competition from C\n                    <jats:sub>2<\/jats:sub>\n                    products. Herein, we demonstrate that a Cu\n                    <jats:sub>2<\/jats:sub>\n                    O\/CeO\n                    <jats:sub>2<\/jats:sub>\n                    interfacial catalyst overcomes these limitations by constructing a *CO\u2500H\n                    <jats:sub>2<\/jats:sub>\n                    O reaction microregion that facilitates selective C\n                    <jats:sub>1<\/jats:sub>\n                    \u2500C\n                    <jats:sub>2<\/jats:sub>\n                    coupling. Isotope\u2010competitive in situ differential electrochemical mass spectrometry (DEMS) reveals that the CeO\n                    <jats:sub>2<\/jats:sub>\n                    \u2010induced interfacial structure shifts protonation pathway of activated CO\n                    <jats:sub>2<\/jats:sub>\n                    from adsorbed hydrogen to solvent hydrogen, thereby generating high local *CO flux. Under CO\n                    <jats:sub>2<\/jats:sub>\n                    RR conditions, the *CO\u2500H\n                    <jats:sub>2<\/jats:sub>\n                    O reaction microregion arises from non\u2212covalent interaction between high\u2010density *CO and loosely H\u2010bonded water molecules. Time\u2010resolved pulsed spectroscopy and theoretical calculations confirmed that this microregion dynamically confines *CO and reduces their molecular orbital degeneracy, enhancing *CO availability for C\u2500C coupling reaction. Site\u2010specific kinetics isotope effect experiments further indicate the reaction microenvironment promotes *CO attack on the \u03b1 carbon of *C\n                    <jats:sub>2<\/jats:sub>\n                    intermediates, effectively steering reaction pathway toward\n                    <jats:italic>n<\/jats:italic>\n                    \u2010propanol. As a result, the catalyst achieves\n                    <jats:italic>n<\/jats:italic>\n                    \u2010propanol Faradaic efficiency (FE) of 26.1%. These findings underscore the significance of non\u2010covalent interactions between intermediates and electrolyte in controlling proton\u2010related surface reaction, offering opportunities for steering electrocatalytic pathways toward valuable products.\n                  <\/jats:p>","DOI":"10.1002\/anie.4139411","type":"journal-article","created":{"date-parts":[[2026,8,5]],"date-time":"2026-08-05T13:50:49Z","timestamp":1785937849000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Unlocking\n                    <i>n<\/i>\n                    \u2010Propanol Electrosynthesis From CO\n                    <sub>2<\/sub>\n                    via Constructing *CO\u2500H\n                    <sub>2<\/sub>\n                    O Reaction Microregion"],"prefix":"10.1002","volume":"65","author":[{"given":"Shanshan","family":"Wu","sequence":"first","affiliation":[{"name":"State Key Laboratory of Natural Product Chemistry College of Chemistry and Chemical Engineering Frontiers Science Center for Rare Isotopes Lanzhou University  Lanzhou China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Zhuang","family":"Zhang","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Natural Product Chemistry College of Chemistry and Chemical Engineering Frontiers Science Center for Rare Isotopes Lanzhou University  Lanzhou China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Zhuoyue","family":"Hou","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Natural Product Chemistry College of Chemistry and Chemical Engineering Frontiers Science Center for Rare Isotopes Lanzhou University  Lanzhou China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Huizhi","family":"Li","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Natural Product Chemistry College of Chemistry and Chemical Engineering Frontiers Science Center for Rare Isotopes Lanzhou University  Lanzhou China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-5446-8889","authenticated-orcid":false,"given":"Yang","family":"Hu","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Natural Product Chemistry College of Chemistry and Chemical Engineering Frontiers Science Center for Rare Isotopes Lanzhou University  Lanzhou China"},{"name":"School of Materials and Energy Electron Microscopy Centre Lanzhou University  Lanzhou China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Nan","family":"Zhang","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Natural Product Chemistry College of Chemistry and Chemical Engineering Frontiers Science Center for Rare Isotopes Lanzhou University  Lanzhou 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