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Yet its efficiency is often constrained because photogenerated electrons recombine before reaching the O\n                    <jats:sub>2<\/jats:sub>\n                    \u2010activation sites. To address this challenge, we developed a thiophene\u2013bipyridine covalent organic framework (BT\u2010Bpy\u2010COF) that localizes photoexcited electrons directly at the catalytic centers. Ultrafast transient absorption spectroscopy and Operando X\u2010ray photoelectron spectroscopy reveal that these confined electrons are rapidly transferred into adsorbed O\n                    <jats:sub>2<\/jats:sub>\n                    , occurring prior to electron\u2010hole recombination. The efficient charge utilization results in markedly enhanced photocatalytic activity. As a result, BT\u2010Bpy\u2010COF achieves an H\n                    <jats:sub>2<\/jats:sub>\n                    O\n                    <jats:sub>2<\/jats:sub>\n                    production rate of 5.3 mmol g\n                    <jats:sup>\u22121<\/jats:sup>\n                    h\n                    <jats:sup>\u22121<\/jats:sup>\n                    under visible light with an apparent quantum yield of 6.74% at 420 nm and a solar\u2010to\u2010chemical conversion efficiency of 0.58%, which is 5.8 times higher than natural photosynthesis. This finding provides a versatile design strategy for advancing high\u2010efficiency and multi\u2010electron photocatalysis.\n                  <\/jats:p>","DOI":"10.1002\/adma.73490","type":"journal-article","created":{"date-parts":[[2026,6,5]],"date-time":"2026-06-05T11:04:08Z","timestamp":1780657448000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":4,"title":["Spatial Confinement of Photogenerated Electrons at Catalytic Sites in Covalent Organic Frameworks for Efficient Photocatalytic H\n                    <sub>2<\/sub>\n                    O\n                    <sub>2<\/sub>\n                    Production"],"prefix":"10.1002","volume":"38","author":[{"given":"Liyang","family":"Qin","sequence":"first","affiliation":[{"name":"State Key Laboratory of Structural Chemistry Fujian Institute of Research on the Structure of Matter Chinese Academy of Sciences  Fuzhou P. R. 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China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-3373-9621","authenticated-orcid":false,"given":"Jian","family":"Zhang","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Structural Chemistry Fujian Institute of Research on the Structure of Matter Chinese Academy of Sciences  Fuzhou P. R. China"},{"name":"University of Chinese Academy of Sciences  Beijing P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Tianhua","family":"Zhou","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Structural Chemistry Fujian Institute of Research on the Structure of Matter Chinese Academy of Sciences  Fuzhou P. R. China"},{"name":"University of Chinese Academy of Sciences  Beijing P. R. China"},{"name":"State Key Laboratory of Chemistry and Utilization of Carbon\u2010Based Energy Resources College of Chemistry Xinjiang University  Urumqi Xinjiang P. R. 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