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We construct a Z\u2010scheme heterojunction consisting of an amorphous vanadium oxide nanolayer on BiVO\n                    <jats:sub>4<\/jats:sub>\n                    nanoparticles (BiVO\n                    <jats:sub>4<\/jats:sub>\n                    \u2010VO\n                    <jats:sub>x<\/jats:sub>\n                    ) for glycerol oxidation by a spatially confined photoelectron deposition method. BiVO\n                    <jats:sub>4<\/jats:sub>\n                    \u2010VO\n                    <jats:sub>x<\/jats:sub>\n                    photoanode achieves a high DHA evolution rate of 400.4\u00a0mmol m\n                    <jats:sup>\u22122<\/jats:sup>\n                    h\n                    <jats:sup>\u22121<\/jats:sup>\n                    and a selectivity of 65.6% at 1.2\u00a0V vs. RHE. Femtosecond transient absorption spectroscopy analysis demonstrates superior charge separation efficiency and ultrafast interfacial transfer kinetics, enabling long\u2010lived photogenerated electrons and holes accumulated in BiVO\n                    <jats:sub>4<\/jats:sub>\n                    conduction band and VO\n                    <jats:sub>x<\/jats:sub>\n                    valence band, respectively. Furthermore, in situ Fourier transform infrared spectroscopy and theoretical calculations reveal that the synergy between the optimized electronic structure of amorphous VO\n                    <jats:sub>x<\/jats:sub>\n                    and Z\u2010scheme heterojunction promotes preferential adsorption of glycerol middle hydroxyl groups and lowers the energy barrier of the rate\u2010determining step, thus facilitating selective DHA production. We fabricated a self\u2010powered device with a DHA productivity of 122.0\u00a0mmol m\n                    <jats:sup>\u22122<\/jats:sup>\n                    h\n                    <jats:sup>\u22121<\/jats:sup>\n                    , a H\n                    <jats:sub>2<\/jats:sub>\n                    productivity of 1.33\u00a0mL cm\n                    <jats:sup>\u22122<\/jats:sup>\n                    h\n                    <jats:sup>\u22121<\/jats:sup>\n                    and a solar\u2010to\u2010H\n                    <jats:sub>2<\/jats:sub>\n                    conversion efficiency of 4.7%. This work highlights the potential of heterojunction engineering for PEC biomass valorization toward value\u2010added products.\n                  <\/jats:p>","DOI":"10.1002\/smll.73167","type":"journal-article","created":{"date-parts":[[2026,3,23]],"date-time":"2026-03-23T11:43:36Z","timestamp":1774266216000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":1,"title":["Ultrafast Electron Transfer at BiVO\n                    <sub>4<\/sub>\n                    \u2010VO\n                    <sub>x<\/sub>\n                    Z\u2010Scheme Interface for Enhanced Selective Oxidation of Glycerol to Dihydroxyacetone"],"prefix":"10.1002","volume":"22","author":[{"given":"Peng","family":"Sun","sequence":"first","affiliation":[{"name":"Beijing Laboratory of New Energy Storage Technology Institute of Energy Power Innovation North China Electric Power University  Beijing P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yunze","family":"Luo","sequence":"additional","affiliation":[{"name":"Beijing Laboratory of New Energy Storage Technology Institute of Energy Power Innovation North China Electric Power University  Beijing P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Ziyuan","family":"Wang","sequence":"additional","affiliation":[{"name":"Beijing Laboratory of New Energy Storage Technology Institute of Energy Power Innovation North China Electric Power University  Beijing P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Xiaoke","family":"Li","sequence":"additional","affiliation":[{"name":"Beijing Laboratory of New Energy Storage Technology Institute of Energy Power Innovation North China Electric Power University  Beijing P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Xijier","family":"Chen","sequence":"additional","affiliation":[{"name":"Beijing Laboratory of New Energy Storage Technology Institute of Energy Power Innovation North China Electric Power University  Beijing P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jianguo","family":"Liu","sequence":"additional","affiliation":[{"name":"Beijing Laboratory of New Energy Storage Technology Institute of Energy Power Innovation North China Electric Power University  Beijing P. R. 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