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Herein, we designed spatially arrayed Cu\n                    <jats:sup>+<\/jats:sup>\n                    \u2010Cu\n                    <jats:sup>0<\/jats:sup>\n                    cluster pairs confined within UiO\u201066 (U66) to achieve spatiotemporally directed CO\n                    <jats:sub>2<\/jats:sub>\n                    hydrogenation to methanol. This architecture was constructed by creating missing\u2010linker defects within U66 using L\u2010ascorbic acid (LA), followed by sequential anchoring of high\u2010density, adjacent Cu\n                    <jats:sup>+<\/jats:sup>\n                    \u2010Cu\n                    <jats:sup>0<\/jats:sup>\n                    cluster pairs (\u22481:1 ratio) to yield a Cu\/U66(LA\u2010Cu) catalyst. Under reaction conditions of 220\u00b0C and 3\u00a0MPa, this catalyst achieved a methanol space\u2010time yield of 688.1 mg\u00b7g\n                    <jats:sup>\u22121<\/jats:sup>\n                    \u00b7h\n                    <jats:sup>\u22121<\/jats:sup>\n                    and an ultra\u2010high methanol selectivity (97.0%). Its unity\u2010methanol selectivity was 1.06\u20131.77 times that of high\u2010stability oxide materials. Meanwhile, catalyst's stability of 200\u00a0h was significantly prolonged compared to high\u2010selectivity MOF\u2010based catalysts that operated stably for 60\u2013175\u00a0h. Mechanistic studies revealed that Cu\n                    <jats:sup>+<\/jats:sup>\n                    \u2010Cu\n                    <jats:sup>0<\/jats:sup>\n                    cluster pairs within defective U66 not only enabled partitioned synergistic activation of CO\n                    <jats:sub>2<\/jats:sub>\n                    and H\n                    <jats:sub>2<\/jats:sub>\n                    , but established an efficient electron\/hydrogen transfer pathway. This facilitated the migration of active hydrogen species to CO\n                    <jats:sub>2<\/jats:sub>\n                    adsorption sites, where adsorbed CO\n                    <jats:sub>2<\/jats:sub>\n                    was converted into CO intermediates and underwent deep hydrogenation. This structural design synergistically enhanced compatibility between H\n                    <jats:sub>2<\/jats:sub>\n                    dissociation and CO\n                    <jats:sub>2<\/jats:sub>\n                    hydrogenation steps, enabling reaction to proceed efficiently along the RWGS + CO\u2010hydro pathway.\n                  <\/jats:p>","DOI":"10.1002\/anie.3440356","type":"journal-article","created":{"date-parts":[[2026,7,21]],"date-time":"2026-07-21T12:11:32Z","timestamp":1784635892000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Cu\n                    <sup>+<\/sup>\n                    \u2010Cu\n                    <sup>0<\/sup>\n                    Cluster Pairs in Defective MOFs for Highly Synergistic CO\n                    <sub>2<\/sub>\n                    Hydrogenation to Methanol"],"prefix":"10.1002","volume":"65","author":[{"given":"Xuehui","family":"Jia","sequence":"first","affiliation":[{"name":"Guangxi Key Laboratory of AI\u2010Driven Zero\u2010Carbon Technology Key Laboratory of New Low\u2010Carbon Green Chemical Technology Education Department of Guangxi Zhuang Autonomous Region School of Chemistry and Chemical Engineering Guangxi University  Nanning People's Republic of China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Weige","family":"Su","sequence":"additional","affiliation":[{"name":"Guangxi Key Laboratory of AI\u2010Driven Zero\u2010Carbon Technology Key Laboratory of New Low\u2010Carbon Green Chemical Technology Education Department of Guangxi Zhuang Autonomous Region School of Chemistry and Chemical Engineering Guangxi University  Nanning People's Republic of China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Changheng","family":"Zhong","sequence":"additional","affiliation":[{"name":"Guangxi Key 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