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To address this challenge, we developed a strategy based on geometric control of spatially confined microenvironments, enabling the rational design of programmable Cu\n                    <jats:sub>x<\/jats:sub>\n                    O microreactors on Cu\n                    <jats:sup>2+<\/jats:sup>\n                    (111)\/Cu\n                    <jats:sup>+<\/jats:sup>\n                    (200) substrates. Two distinct catalyst architectures\u2014small\u2010ordered (s\u2010Cu\n                    <jats:sub>x<\/jats:sub>\n                    O@styrene) and large\u2010ordered (c\u2010Cu\n                    <jats:sub>x<\/jats:sub>\n                    O@styrene)\u2014were systematically engineered to modulate CO intermediate behavior, thereby directing reaction selectivity toward ethylene and ethanol production. Faradaic efficiencies for C\n                    <jats:sub>2+<\/jats:sub>\n                    products demonstrate pronounced dependence on microstructure: increasing from negligible values in the small\u2010ordered s\u2010Cu\n                    <jats:sub>x<\/jats:sub>\n                    O@styrene (25.6% ethylene,12.4% ethanol, 3% propylene) to 78.8% in the large\u2010ordered c\u2010Cu\n                    <jats:sub>x<\/jats:sub>\n                    O@styrene (55% ethylene, 23% ethanol, 1% propylene). In situ infrared spectroscopy reveals that the highly ordered configuration enhances CO adsorption, promoting the accumulation of critical *OCCOH and *OC\n                    <jats:sub>2<\/jats:sub>\n                    H\n                    <jats:sub>5<\/jats:sub>\n                    intermediates. Moreover, synergistic interactions between Cu\n                    <jats:sup>+<\/jats:sup>\n                    and Cu\n                    <jats:sup>0<\/jats:sup>\n                    active sites accelerate C\u2013C coupling kinetics, favoring selective formation of C\n                    <jats:sub>2+<\/jats:sub>\n                    species. This work establishes a geometry\u2010driven paradigm for controlling catalytic selectivity independent of compositional tuning, offering a promising avenue for the development of adaptive catalytic systems in renewable energy conversion.\n                  <\/jats:p>","DOI":"10.1002\/smll.73668","type":"journal-article","created":{"date-parts":[[2026,5,6]],"date-time":"2026-05-06T08:45:26Z","timestamp":1778057126000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":1,"title":["A Confined Cu\n                    <sub>x<\/sub>\n                    O@Styrene Microreactor Achieves the Conversion of CO\n                    <sub>2<\/sub>\n                    to C\n                    <sub>2+<\/sub>\n                    Products via Intermediate Trapping"],"prefix":"10.1002","volume":"22","author":[{"given":"Jiaxin","family":"Bai","sequence":"first","affiliation":[{"name":"State Key Laboratory of High\u2010efficiency Coal Utilization and Green Chemical Engineering School of Chemistry and Chemical Engineering Ningxia University  Yinchuan Ningxia P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Xueru","family":"Zhao","sequence":"additional","affiliation":[{"name":"State Key Laboratory of High\u2010efficiency Coal Utilization and Green Chemical Engineering School of Chemistry and Chemical Engineering Ningxia University  Yinchuan Ningxia P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jinlong","family":"Wu","sequence":"additional","affiliation":[{"name":"State Key Laboratory of High\u2010efficiency Coal Utilization and Green Chemical Engineering School of Chemistry and Chemical Engineering Ningxia University  Yinchuan Ningxia P. R. 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