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Herein, a class of hydroxyl groups (\u2500OH) functionalized covalent organic framework (COF) is reported as a proton reservoir to compensate ORR for greatly improving the efficiency of H\n                    <jats:sub>2<\/jats:sub>\n                    O\n                    <jats:sub>2<\/jats:sub>\n                    photosynthesis. It has been demonstrated that the incorporation of \u2500OH into the TFBP\u2010DHBD (TFBP: 1,2,4,5\u2010tetrakis\u2010(4\u2010formylphenyl)benzene, DHBD: 3,3\u2032\u2010dihydroxybenzidine) COF can achieve a 3.3 times higher H\n                    <jats:sub>2<\/jats:sub>\n                    O\n                    <jats:sub>2<\/jats:sub>\n                    photosynthetic activity than that of TFBP\u2010BD (BD: benzidine) COF without \u2500OH groups. Isotope labeling experiments and in situ infrared spectroscopy analysis demonstrate that the proton reservoir can donate protons for ORR and subsequently regain the released protons from WOR. Theoretical calculations further confirm that the \u2500OH functionalized COF provides the protons for the formation of *OOH intermediate and reduces its energy barrier, thereby facilitating the photosynthesis of H\n                    <jats:sub>2<\/jats:sub>\n                    O\n                    <jats:sub>2<\/jats:sub>\n                    . A novel COF loaded with Al\n                    <jats:sub>2<\/jats:sub>\n                    O\n                    <jats:sub>3<\/jats:sub>\n                    spheres\u2010based streamlined microreactor is built that can simultaneously achieve production of H\n                    <jats:sub>2<\/jats:sub>\n                    O\n                    <jats:sub>2<\/jats:sub>\n                    and elimination of bacteria over 1.3\u00a0\u00d7\u00a010\n                    <jats:sup>4<\/jats:sup>\n                    CFU mL\n                    <jats:sup>\u22121<\/jats:sup>\n                    , superior to the reported continuous flow photocatalytic reactors.\n                  <\/jats:p>","DOI":"10.1002\/adma.202502990","type":"journal-article","created":{"date-parts":[[2025,4,1]],"date-time":"2025-04-01T02:55:06Z","timestamp":1743476106000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":75,"title":["Proton Reservoir in Covalent Organic Framework Compensating Oxygen Reduction Reaction Enhances Hydrogen Peroxide Photosynthesis"],"prefix":"10.1002","volume":"37","author":[{"given":"Chenglong","family":"Sun","sequence":"first","affiliation":[{"name":"School of Materials Science and Engineering Peking University  Beijing 100871 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Ying","family":"Han","sequence":"additional","affiliation":[{"name":"School of Materials Science and Engineering Peking University  Beijing 100871 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Hongyu","family":"Guo","sequence":"additional","affiliation":[{"name":"School of Materials Science and Engineering Peking University  Beijing 100871 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Rui","family":"Zhao","sequence":"additional","affiliation":[{"name":"School of Materials Science and Engineering Peking University  Beijing 100871 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Engineering Peking University  Beijing 100871 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Mingchuan","family":"Luo","sequence":"additional","affiliation":[{"name":"School of Materials Science and Engineering Peking University  Beijing 100871 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5941-414X","authenticated-orcid":false,"given":"Shaojun","family":"Guo","sequence":"additional","affiliation":[{"name":"School of Materials Science and Engineering Peking University  Beijing 100871 China"},{"name":"Beijing Innovation Centre for Engineering Science and Advanced Technology Peking University  Beijing 100871 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