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Nevertheless, low efficiency of multielectron utilization and high C\u2500C coupling energy barrier cause poor performance in C\n                    <jats:sub>2<\/jats:sub>\n                    H\n                    <jats:sub>5<\/jats:sub>\n                    OH production. Here, we report a TiO\n                    <jats:sub>2\u2212x<\/jats:sub>\n                    \/BNF (boron nitride flower) S\u2010scheme heterojunction microreactor to steer the asymmetric Ti active sites configuration and redox potential, thereby enhancing the thermodynamic and kinetic formation of C\n                    <jats:sub>2<\/jats:sub>\n                    H\n                    <jats:sub>5<\/jats:sub>\n                    OH. The S\u2010scheme TiO\n                    <jats:sub>2\u2212x<\/jats:sub>\n                    \/BNF heterostructure provides spatially separated sites for CO\n                    <jats:sub>2<\/jats:sub>\n                    reduction and water oxidation with efficient charge carrier utilization. The flower\u2010like structure of BNF improves the local concentration of *CO within microreactors originated from confinement effect to satisfy the coupling process. Self\u2010generated oxygen vacancy in TiO\n                    <jats:sub>2\u2212x<\/jats:sub>\n                    brought by BNF leads to different electron densities of adjacent Ti sites, which strengthens the adsorption of *CO and reduces the *CO\u2010CHO formation energy. C\n                    <jats:sub>2<\/jats:sub>\n                    H\n                    <jats:sub>5<\/jats:sub>\n                    OH dehydration is often difficult within the hydrophilic TiO\n                    <jats:sub>2\u2212x<\/jats:sub>\n                    \/BNF microreactor, thus it tends to produce C\n                    <jats:sub>2<\/jats:sub>\n                    H\n                    <jats:sub>5<\/jats:sub>\n                    OH rather than C\n                    <jats:sub>2<\/jats:sub>\n                    H\n                    <jats:sub>4<\/jats:sub>\n                    . Through the synergizing effects, the well\u2010constructed microreactor delivers an excellent C\n                    <jats:sub>2<\/jats:sub>\n                    H\n                    <jats:sub>5<\/jats:sub>\n                    OH production rate of 51.4 \u00b5mol g\n                    <jats:sup>\u22121<\/jats:sup>\n                    h\n                    <jats:sup>\u22121<\/jats:sup>\n                    with a selectivity of 99% and unprecedented global stability. Our work can serve as inspiration for developing Ti\u2010based catalysts for CO\n                    <jats:sub>2<\/jats:sub>\n                    conversion to C\n                    <jats:sub>2<\/jats:sub>\n                    H\n                    <jats:sub>5<\/jats:sub>\n                    OH using solar energy.\n                  <\/jats:p>","DOI":"10.1002\/anie.202522838","type":"journal-article","created":{"date-parts":[[2025,11,10]],"date-time":"2025-11-10T13:35:02Z","timestamp":1762781702000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":10,"title":["Ethanol Synthesis by CO\n                    <sub>2<\/sub>\n                    Photoreduction Catalyzed by Self\u2010Optimized Ti\n                    <sup>\u03b4+<\/sup>\n                    \u2010Based Heterojunction"],"prefix":"10.1002","volume":"65","author":[{"given":"Zhehao","family":"Liu","sequence":"first","affiliation":[{"name":"Institute for Energy Research School of Chemistry and Chemical Engineering Jiangsu University  Zhenjiang Jiangsu 212013 P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Liang","family":"Mao","sequence":"additional","affiliation":[{"name":"School of Materials Science and Physics China University of Mining and Technology  Xuzhou 221116 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Zheyang","family":"Liu","sequence":"additional","affiliation":[{"name":"Institute for Energy Research School of Chemistry and Chemical Engineering Jiangsu University  Zhenjiang Jiangsu 212013 P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Min","family":"Zhou","sequence":"additional","affiliation":[{"name":"Institute for Energy Research School of Chemistry and Chemical Engineering Jiangsu University  Zhenjiang Jiangsu 212013 P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Huilin","family":"Wang","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Rare Earth Resource Utilization Changchun Institute of Applied Chemistry Chinese Academy of Sciences  Changchun 130022 P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jing","family":"Li","sequence":"additional","affiliation":[{"name":"Key Laboratory of Photochemical Conversion and Optoelectronic Materials Technical Institute of Physics and Chemistry Chinese Academy of Sciences  Beijing 100190 P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Rui","family":"Zhang","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Rare Earth Resource Utilization Changchun Institute of Applied Chemistry Chinese Academy of Sciences  Changchun 130022 P. R. 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