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Herein, we propose to produce CO and H<jats:sub>2<\/jats:sub> from biomass via a divided photoelectrochemical (PEC) cell at room temperature. Nitrogen doped tungsten trioxide (N\u2010WO<jats:sub>3<\/jats:sub>) photoanode reforms biopolyols to CO and H<jats:sup>+<\/jats:sup>, and platinum cathode reduces H<jats:sup>+<\/jats:sup> to H<jats:sub>2<\/jats:sub>, achieving CO evolution rate of 45\u2005mmol\u2009m<jats:sup>\u22122<\/jats:sup>\u2009h<jats:sup>\u22121<\/jats:sup> (&gt;75\u2009% gas selectivity) and H<jats:sub>2<\/jats:sub> evolution rate of 237\u2005mmol\u2009m<jats:sup>\u22122<\/jats:sup>\u2009h<jats:sup>\u22121<\/jats:sup> with purity &gt;99.99\u2009% from glycerol. The nitrogen doping induces structure polarity of WO<jats:sub>3<\/jats:sub> photoanode, leading to the formation of an internal electric field which promotes the separation and transfer of the photoinduced charges and improves PEC efficiency. A wide range of biopolyols, such as ethylene glycol, xylose, fructose, glucose, sucrose, lactose, maltose, and inulin were effectively converted into CO and H<jats:sub>2<\/jats:sub>. This work provides a promising method to produce highly pure H<jats:sub>2<\/jats:sub> together with CO from biomass.<\/jats:p>","DOI":"10.1002\/anie.202210745","type":"journal-article","created":{"date-parts":[[2022,8,29]],"date-time":"2022-08-29T02:39:58Z","timestamp":1661740798000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":69,"title":["Photoelectrocatalytic Reforming of Polyol\u2010based Biomass into CO and H<sub>2<\/sub> over Nitrogen\u2010doped WO<sub>3<\/sub> with Built\u2010in Electric Fields"],"prefix":"10.1002","volume":"61","author":[{"given":"Fanhao","family":"Kong","sequence":"first","affiliation":[{"name":"Zhang Dayu School of Chemistry Dalian University of Technology  Dalian 116024, Liaoning China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Hongru","family":"Zhou","sequence":"additional","affiliation":[{"name":"Zhang Dayu School of Chemistry Dalian University of Technology  Dalian 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