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In this study, the rational manipulation of Cu defect sites was realized for the selective formation of C\n                    <jats:sub>2<\/jats:sub>\n                    H\n                    <jats:sub>5<\/jats:sub>\n                    OH and C\n                    <jats:sub>2<\/jats:sub>\n                    H\n                    <jats:sub>4<\/jats:sub>\n                    . Low\u2010coordination amorphous and medium\u2010coordination grain\u2010boundary Cu defect sites with different *OH affinity were found to play a decisive role in the selective protonation of CH\n                    <jats:sub>2<\/jats:sub>\n                    CHO*. In particular, grain\u2010boundary\u2010rich Cu (denoted as Cu\u20101) that weakly adsorbed *OH and CH\n                    <jats:sub>2<\/jats:sub>\n                    CHO* favored the protonation on \u03b2\u2010C of CH\n                    <jats:sub>2<\/jats:sub>\n                    CHO*, leading to the selective production of C\n                    <jats:sub>2<\/jats:sub>\n                    H\n                    <jats:sub>5<\/jats:sub>\n                    OH. In contrast, amorphous Cu defect sites (denoted as Cu\u20103) showed strong *OH adsorption and then strong CH\n                    <jats:sub>2<\/jats:sub>\n                    CHO* adsorption, facilitating C\u2212O breaking and C\n                    <jats:sub>2<\/jats:sub>\n                    H\n                    <jats:sub>4<\/jats:sub>\n                    formation. In the membrane electrode assembly (MEA) configuration, a remarkably high full\u2010cell energy efficiency (EE) of 29.0\u2009% for C\n                    <jats:sub>2<\/jats:sub>\n                    H\n                    <jats:sub>5<\/jats:sub>\n                    OH on Cu\u20101 and an impressive high full\u2010cell EE of 25.6\u2009% for C\n                    <jats:sub>2<\/jats:sub>\n                    H\n                    <jats:sub>4<\/jats:sub>\n                    on Cu\u20103 were observed. In addition, a C\n                    <jats:sub>2<\/jats:sub>\n                    H\n                    <jats:sub>4<\/jats:sub>\n                    Faradaic efficiency (FE) of 63.4\u00b11.5\u2009% was achieved on Cu\u20103 at a notable current of 12.5\u2005A with a 25\u2005cm\n                    <jats:sup>\u22122<\/jats:sup>\n                    MEA configuration. These results provided crucial insights into the significance of defect sites in manipulating the adsorption of *OH for the selective production of C\n                    <jats:sub>2<\/jats:sub>\n                    H\n                    <jats:sub>4<\/jats:sub>\n                    or C\n                    <jats:sub>2<\/jats:sub>\n                    H\n                    <jats:sub>5<\/jats:sub>\n                    OH.\n                  <\/jats:p>","DOI":"10.1002\/anie.202501773","type":"journal-article","created":{"date-parts":[[2025,2,15]],"date-time":"2025-02-15T06:02:06Z","timestamp":1739599326000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":90,"title":["Selective Electrochemical CO\n                    <sub>2<\/sub>\n                    Reduction to Ethylene or Ethanol via Tuning *OH Adsorption"],"prefix":"10.1002","volume":"64","author":[{"given":"Dazhong","family":"Zhong","sequence":"first","affiliation":[{"name":"College of Chemistry and Chemical Engineering Shanxi Key Laboratory of Gas Energy Efficient and Clean Utilization Taiyuan University of Technology  Taiyuan 030024, Shanxi P.\u2005R. 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