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The construction of efficient catalytic sites and the maintenance of the site stability are crucial to achieving high\u2010efficiency conversion of CO\n                    <jats:sub>2<\/jats:sub>\n                    \u2010to\u2010CH\n                    <jats:sub>4<\/jats:sub>\n                    . Herein, we design a La\n                    <jats:sub>2<\/jats:sub>\n                    O\n                    <jats:sub>3<\/jats:sub>\n                    \u2010supported oxygen\u2010containing Cu clusters functionalized with hexanethiol (HT) molecules catalyst (HT@O\u2010Cu\n                    <jats:sub>c<\/jats:sub>\n                    \/La\n                    <jats:sub>2<\/jats:sub>\n                    O\n                    <jats:sub>3<\/jats:sub>\n                    ), achieving a high CH\n                    <jats:sub>4<\/jats:sub>\n                    Faradaic efficiency (FE\n                    <jats:sub>CH4<\/jats:sub>\n                    ) of 77.8% with a partial current density of 389.2\u00a0mA cm\n                    <jats:sup>\u22122<\/jats:sup>\n                    , and demonstrating excellent stability over a 250 h operation period. The thiol\u2010ligand was modified at the interface between O\u2010Cu\n                    <jats:sub>c<\/jats:sub>\n                    and La\n                    <jats:sub>2<\/jats:sub>\n                    O\n                    <jats:sub>3<\/jats:sub>\n                    via S\u2010coordination, enabling electron transfer between La and Cu sites and establishing a stable electronic supplementary channel that continuously stabilizes the low\u2010coordinated Cu\n                    <jats:sup>\u03b4+<\/jats:sup>\n                    (0.4 &lt; \u03b4 &lt; 0.5) active state during the electrochemical process. Moreover, mechanistic studies reveal that the ligand modification optimizes *CO adsorption on Cu sites and steers *CHO hydrogenation toward *CH\n                    <jats:sub>2<\/jats:sub>\n                    OH. The electronic channel effect can strengthen the bond energy of Cu\u2013C, facilitating the desorption of *OH. The La\u2010mediated water activation generates abundant protons, which drives the *CH\n                    <jats:sub>2<\/jats:sub>\n                    \u2500*CH\n                    <jats:sub>3<\/jats:sub>\n                    \u2500*CH\n                    <jats:sub>4<\/jats:sub>\n                    directional hydrogenation step, ultimately achieving highly selective CH\n                    <jats:sub>4<\/jats:sub>\n                    production.\n                  <\/jats:p>","DOI":"10.1002\/anie.7136576","type":"journal-article","created":{"date-parts":[[2026,4,20]],"date-time":"2026-04-20T05:40:33Z","timestamp":1776663633000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Ligand Protection Strategy for Highly Selective and Stable Electrochemical CO\n                    <sub>2<\/sub>\n                    Methanation"],"prefix":"10.1002","volume":"65","author":[{"given":"Wenshan","family":"Gao","sequence":"first","affiliation":[{"name":"College of Chemistry and Chemical Engineering Qingdao University  Qingdao China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Zhijun","family":"Zhu","sequence":"additional","affiliation":[{"name":"College of Chemistry and Chemical Engineering Qingdao University  Qingdao China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Qian","family":"Gong","sequence":"additional","affiliation":[{"name":"College of Chemistry and Chemical Engineering Qingdao University  Qingdao China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jingyu","family":"Si","sequence":"additional","affiliation":[{"name":"College of Chemistry and Chemical Engineering Qingdao University  Qingdao 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