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We address this challenge through the atomic\u2010scale copper (Cu) clusters anchored on carbon\u2010doped potassium poly(heptazine imide) (Cu\/C\u2010K\u2010PHI). Carbon doping extends the \u03c0\u2010conjugation within poly(heptazine imide) framework, narrowing optical bandgap to 1.89 eV, suppressing photogenerated charge\u2010carrier recombination and enhancing interfacial charge transfer. The anchored Cu clusters lower the kinetic barrier for C\u2500C coupling. Focused on the liquid\u2010phase C\u2500C coupling pathway, Cu\/C\u2010K\u2010PHI selectively produces ethanol with \u223c100% selectivity among liquid\u2010phase products, exhibiting production rate of 18.98 \u00b5mol g\n                    <jats:sup>\u22121<\/jats:sup>\n                    h\n                    <jats:sup>\u22121<\/jats:sup>\n                    , reaching 77.01 \u00b5mol g\n                    <jats:sup>\u22121<\/jats:sup>\n                    after 4 h and retaining \u223c98% of its activity over five cycles under 1\u2010sun illumination without sacrificial agents. The solar\u2010to\u2010ethanol conversion efficiency is 0.175% with apparent quantum yield is 0.516%. In situ attenuated total reflectance\u2010infrared spectra, together with density functional theory calculations, reveal O*C\u2500CO\u2010mediated *CO dimerization pathway, providing a mechanistic origin for CO\n                    <jats:sub>2<\/jats:sub>\n                    \u2010to\u2010C\n                    <jats:sub>2<\/jats:sub>\n                    H\n                    <jats:sub>5<\/jats:sub>\n                    OH selectivity. These results show that synergistic electronic\u2010structure modulation and atomic\u2010scale metal engineering can steer CO\n                    <jats:sub>2<\/jats:sub>\n                    photoreduction selectively toward ethanol under mild conditions without sacrificial agents.\n                  <\/jats:p>","DOI":"10.1002\/smll.73424","type":"journal-article","created":{"date-parts":[[2026,4,22]],"date-time":"2026-04-22T07:15:12Z","timestamp":1776842112000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Selective Solar CO\n                    <sub>2<\/sub>\n                    Conversion into Ethanol Using Atomic\u2010Scale Copper Clusters Anchored \u03c0\u2010extended Poly(heptazine imide)"],"prefix":"10.1002","volume":"22","author":[{"given":"Muhammad Zaeem Azam","family":"Khan","sequence":"first","affiliation":[{"name":"Carbon Resources Conversion Research Center Korea Institute of Energy Technology (KENTECH)  Naju Republic of Korea"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Shanmugasundaram","family":"Kamalakannan","sequence":"additional","affiliation":[{"name":"Universit\u00e9 Gustave Eiffel COSYS\/IMSE  Champs Sur Marne France"},{"name":"Center of Excellence in Materials for Advanced Technologies (CeMAT) SRM Institute of Science and Technology, Kattankulathur  Chengalpattu Tamil Nadu India"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Ramesh Poonchi","family":"Sivasankaran","sequence":"additional","affiliation":[{"name":"Carbon Resources Conversion Research Center Korea Institute of Energy Technology (KENTECH)  Naju Republic of Korea"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Amol Uttam","family":"Pawar","sequence":"additional","affiliation":[{"name":"Carbon Resources Conversion Research Center Korea Institute of Energy Technology (KENTECH)  Naju Republic of Korea"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Sanjeev","family":"Gupta","sequence":"additional","affiliation":[{"name":"Carbon Resources Conversion Research Center Korea Institute of Energy Technology (KENTECH)  Naju Republic of Korea"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Sung\u2010hoon","family":"Oh","sequence":"additional","affiliation":[{"name":"Carbon Resources Conversion Research Center Korea Institute of Energy Technology (KENTECH)  Naju Republic of Korea"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Young Seok","family":"Son","sequence":"additional","affiliation":[{"name":"Carbon Resources Conversion Research Center Korea Institute of Energy Technology (KENTECH)  Naju Republic of Korea"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Minseong","family":"Kim","sequence":"additional","affiliation":[{"name":"Carbon Resources Conversion Research Center Korea Institute of Energy Technology (KENTECH)  Naju Republic of Korea"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Sachin G.","family":"Ghugal","sequence":"additional","affiliation":[{"name":"Carbon Resources Conversion Research Center Korea Institute of Energy Technology (KENTECH)  Naju Republic of Korea"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Kyoung Mo","family":"Park","sequence":"additional","affiliation":[{"name":"Carbon Resources Conversion Research Center Korea Institute of Energy Technology (KENTECH)  Naju Republic of Korea"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Hongxian","family":"Han","sequence":"additional","affiliation":[{"name":"Laboratory of Catalysis for Energy and Resources College of Sciences Yanbian University  Yanji Jilin Province P. 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