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However, extant Cu clusters employed in the CO\n                    <jats:sub>2<\/jats:sub>\n                    RR predominantly yield 2e\n                    <jats:sup>\u2212<\/jats:sup>\n                    products. Herein, two model Cu\n                    <jats:sub>4<\/jats:sub>\n                    (MMI)\n                    <jats:sub>4<\/jats:sub>\n                    and Cu\n                    <jats:sub>8<\/jats:sub>\n                    (MMI)\n                    <jats:sub>4<\/jats:sub>\n                    (\n                    <jats:sup>\n                      <jats:italic>t<\/jats:italic>\n                    <\/jats:sup>\n                    BuS)\n                    <jats:sub>4<\/jats:sub>\n                    clusters (MMI=2\u2010mercapto\u20101\u2010methylimidazole) are prepared to investigate the synergistic effect of Cu\n                    <jats:sup>+<\/jats:sup>\n                    and adjacent S sites on the CO\n                    <jats:sub>2<\/jats:sub>\n                    RR. Cu\n                    <jats:sub>4<\/jats:sub>\n                    (MMI)\n                    <jats:sub>4<\/jats:sub>\n                    can reduce CO\n                    <jats:sub>2<\/jats:sub>\n                    to deep\u2010reduced products with a 91.0\u2009% Faradaic efficiency (including 53.7\u2009% for CH\n                    <jats:sub>4<\/jats:sub>\n                    ) while maintaining remarkable stability. Conversely, Cu\n                    <jats:sub>8<\/jats:sub>\n                    (MMI)\n                    <jats:sub>4<\/jats:sub>\n                    (\n                    <jats:sup>\n                      <jats:italic>t<\/jats:italic>\n                    <\/jats:sup>\n                    BuS)\n                    <jats:sub>4<\/jats:sub>\n                    shows a remarkable preference for C\n                    <jats:sub>2+<\/jats:sub>\n                    products, achieving a maximum FE of 58.5\u2009% with a C\n                    <jats:sub>2+<\/jats:sub>\n                    current density of 152.1\u2005mA\u22c5cm\n                    <jats:sup>\u22122<\/jats:sup>\n                    . In situ XAS and ex situ XPS spectra reveal the preservation of Cu\n                    <jats:sup>+<\/jats:sup>\n                    species in Cu clusters during CO\n                    <jats:sub>2<\/jats:sub>\n                    RR, extensively enhancing the adsorption capacity of *CO intermediate. Moreover, kinetic analysis and theoretical calculations confirm that S sites facilitate H\n                    <jats:sub>2<\/jats:sub>\n                    O dissociation into *H species, which directly participate in the protonation process on adjacent Cu sites for the protonation of *CO to *CHO. This study highlights the important role of Cu\u2212S dual sites in Cu clusters and provides mechanistic insights into the CO\n                    <jats:sub>2<\/jats:sub>\n                    RR pathway at the atomic level.\n                  <\/jats:p>","DOI":"10.1002\/anie.202412144","type":"journal-article","created":{"date-parts":[[2024,8,21]],"date-time":"2024-08-21T23:19:27Z","timestamp":1724282367000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":76,"title":["Promoting CO\n                    <sub>2<\/sub>\n                    Electroreduction to Hydrocarbon Products via Sulfur\u2010Enhanced Proton Feeding in Atomically Precise Thiolate\u2010Protected Cu Clusters"],"prefix":"10.1002","volume":"63","author":[{"given":"Jun\u2010Kang","family":"Li","sequence":"first","affiliation":[{"name":"Henan Key Laboratory of Crystalline Molecular Functional Materials College of Chemistry and Pingyuan Laboratory Zhengzhou University  Zhengzhou 450001 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jian\u2010Peng","family":"Dong","sequence":"additional","affiliation":[{"name":"Henan Key Laboratory of Crystalline Molecular Functional Materials College of Chemistry and Pingyuan Laboratory Zhengzhou University  Zhengzhou 450001 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Shuang\u2010Shuang","family":"Liu","sequence":"additional","affiliation":[{"name":"Henan Key Laboratory of Crystalline Molecular Functional Materials College of Chemistry and Pingyuan Laboratory Zhengzhou University  Zhengzhou 450001 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yue","family":"Hua","sequence":"additional","affiliation":[{"name":"Henan Key Laboratory of Crystalline Molecular Functional Materials College of Chemistry and Pingyuan Laboratory Zhengzhou University  Zhengzhou 450001 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Xue\u2010Li","family":"Zhao","sequence":"additional","affiliation":[{"name":"Henan Key Laboratory of Crystalline Molecular Functional Materials College of Chemistry and Pingyuan Laboratory Zhengzhou University  Zhengzhou 450001 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Zhongjun","family":"Li","sequence":"additional","affiliation":[{"name":"Henan Key Laboratory of Crystalline Molecular Functional Materials College of Chemistry and Pingyuan Laboratory Zhengzhou University  Zhengzhou 450001 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Shu\u2010Na","family":"Zhao","sequence":"additional","affiliation":[{"name":"Henan Key Laboratory of Crystalline Molecular Functional Materials College of Chemistry and Pingyuan Laboratory Zhengzhou University  Zhengzhou 450001 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-6728-0559","authenticated-orcid":false,"given":"Shuang\u2010Quan","family":"Zang","sequence":"additional","affiliation":[{"name":"Henan Key Laboratory of Crystalline Molecular Functional Materials College of Chemistry and Pingyuan Laboratory Zhengzhou University  Zhengzhou 450001 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Rui","family":"Wang","sequence":"additional","affiliation":[{"name":"Henan Key Laboratory of Crystalline Molecular Functional Materials College of Chemistry and Pingyuan Laboratory Zhengzhou University  Zhengzhou 450001 China"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2024,10,17]]},"reference":[{"key":"e_1_2_8_1_1","unstructured":"\u00a0"},{"key":"e_1_2_8_2_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202110657"},{"key":"e_1_2_8_3_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.0c11450"},{"key":"e_1_2_8_4_2","doi-asserted-by":"publisher","DOI":"10.1002\/adma.201805405"},{"key":"e_1_2_8_5_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202105118"},{"key":"e_1_2_8_6_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202116706"},{"key":"e_1_2_8_7_1","unstructured":"\u00a0"},{"key":"e_1_2_8_8_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.9b12445"},{"key":"e_1_2_8_9_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202205626"},{"key":"e_1_2_8_10_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202306822"},{"key":"e_1_2_8_11_2","author":"Huang K.-Y.","year":"2024","journal-title":"J. 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