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Replacing water oxidation with oxidation of organic molecules emerges as an attractive strategy to enhance the hydrogen production efficiency of PEC systems while generating value\u2010added anodic products. Here, a PEC system utilizing a Mo, N co\u2010doped BiVO\n                    <jats:sub>4<\/jats:sub>\n                    photoanode and NaClO\n                    <jats:sub>4<\/jats:sub>\n                    electrolyte for the glycerol oxidation reaction to approaching the theoretical limit of current doubling that enables a two\u2010electron reaction to be driven by a single photon, is reported. While nitrogen doping optimizes the bulk charge separation\/transport performance of Mo\u2010doped BiVO\n                    <jats:sub>4<\/jats:sub>\n                    photoanodes, NaClO\n                    <jats:sub>4<\/jats:sub>\n                    as the supporting electrolyte further enhances the reaction kinetics and surface charge extraction efficiency. The optimized system reaches a record photocurrent density of 9.73\u00a0mA\u00a0cm\n                    <jats:sup>\u22122<\/jats:sup>\n                    at 1.23\u00a0V versus RHE and a maximum internal quantum efficiency of 182%. It predominantly produces C\u2010C cleavage products, including glycolaldehyde and formaldehyde, and can maintain stable performance for over 500\u00a0h. DFT calculations reveal that glycerol can undergo adjacent hydroxyl bidentate chelation adsorption on the BiVO\n                    <jats:sub>4<\/jats:sub>\n                    surface. This system is applicable for the current doubling reaction of various polyhydroxy alcohols, providing a potential pathway for efficient valorization of platform molecules and effective recycling of waste plastics.\n                  <\/jats:p>","DOI":"10.1002\/adma.202516504","type":"journal-article","created":{"date-parts":[[2025,11,5]],"date-time":"2025-11-05T14:12:50Z","timestamp":1762351970000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":12,"title":["Photoelectrochemical Glycerol Valorization Achieving an Internal Quantum Efficiency Over 180% via Current Doubling"],"prefix":"10.1002","volume":"38","author":[{"given":"Zihao","family":"Wu","sequence":"first","affiliation":[{"name":"Beijing National Laboratory for Molecular Science (BNLMS), College of Chemistry and Molecular Engineering Peking University  Beijing 100871 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