Selective Dehydrogenative Coupling of Furfuryl Alcohol Using an Fe‐Containing Polyoxometalates/CdS Photocatalytic System

Photocatalytic dehydrogenative coupling of biomass‐derived furfuryl alcohol (FA) provides a promising route for simultaneous biomass upgrading and solar‐to‐chemical energy conversion. Herein, two novel isostructural Fe‐containing polyoxometalates (POMs), Fe II 2 (H 2 O) 6 H 19 [Fe III 7 Sb V 4 (H 2 O) 12 W 6 O 20 K 2 (C 4 H 2 O 6 ) 2 (B‐ β ‐Sb III W 9 O 33 ) 6 ]·55H 2 O ( 1 ) and Fe II 2 (H 2 O) 6 Na 4 H 11.8 [Fe III 8.6 (H 2 O) 16 W 8.4 O 22 Na 2 (B‐ β ‐Bi III W 9 O 33 ) 6 ]·41H 2 O ( 2 ), were synthesized via a one‐pot solvothermal method and coupled with CdS nanorods (CdS NRs) to construct hybrid photocatalysts for FA conversion under 450 nm LED irradiation. Among them, 1/ CdS exhibited superior performance, achieving 78.95% FA conversion, 85.91% selectivity toward hydrofuroin (HDF), and efficient H 2 evolution (13.49 μmol). Structural and mechanistic studies revealed that the synergistic interaction between CdS NRs and Fe‐containing POMs promotes charge separation and migration, thereby enhancing photocatalytic efficiency. This work highlights the potential of transition‐metal‐functionalized POMs for integrated biomass valorization and solar fuel production.