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Here we report a benzoxazine\u2010based <jats:italic>m<\/jats:italic>\u2010aminophenol\u2010formaldehyde resin (APFac) polymerized at ambient conditions, exhibiting superior H<jats:sub>2<\/jats:sub>O<jats:sub>2<\/jats:sub> yield and long\u2010term stability to most polymeric photocatalysts. Benzoxazine structure was identified as the crucial photocatalytic active segment in APFac. Favorable adsorption of oxygen\/intermediates on benzoxazine structure and commendable product selectivity accelerated the reaction kinetically in stepwise single\u2010electron oxygen reduction reaction. The proposed benzoxazine\u2010based phenolic resin provides the possibility of production in batches and industrial application, and sheds light on the de novo design and analysis of metal\u2010free polymeric photocatalysts.<\/jats:p>","DOI":"10.1002\/anie.202302829","type":"journal-article","created":{"date-parts":[[2023,3,25]],"date-time":"2023-03-25T20:03:20Z","timestamp":1679774600000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":112,"title":["Ambient Preparation of Benzoxazine\u2010based Phenolic Resins Enables Long\u2010term Sustainable Photosynthesis of Hydrogen Peroxide"],"prefix":"10.1002","volume":"62","author":[{"given":"Xinyao","family":"Wang","sequence":"first","affiliation":[{"name":"State Key Laboratory of Catalysis Dalian Institute of Chemical Physics Chinese Academy of Sciences  Dalian 116023 China"},{"name":"Center of Materials Science and Optoelectronics Engineering University of Chinese Academy of Sciences  Beijing 100049 P. 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