Photocatalytic C-O activation and biomass derived polymer precursor production with CO2 over redox centers spatially separated Sv-ZnIn2S4/BiVO4

It is a very important, promising and challenging exploration to achieve the CO2 transformation and renewable biomass utilization for value added chemical intermediate production. Herein, S vacancies enriched Z-scheme Sv-ZnIn2S4/BiVO4 was designed to achieve photocatalytic C-O activation and carboxylation with CO2 in the absence of sacrificial agent. Various aromatic alcohols could be utilized to prepare corresponding carbon chain increased aryl carboxylic acids through acetic anhydride assisted esterification, photogenerated holes oxidization induced benzyl radical generation and subsequent CO2 carboxylation. It is worth mentioning that furfuryl alcohol could also achieve the C-O activation and di-carboxylation to prepare biomass derived polymer precursor. In Z-scheme Sv-ZnIn2S4/BiVO4, spatially separating redox centers construction enhanced photogenerated holes and electrons separation was favorable for the benzyl radical generation and CO2 carboxylation. Moreover, the introduction of S vacancies was helpful for the photoinduced electrons enrichment and substrate capture ability improvement.