Abstract Light‐driven photocatalytic conversion of biomass‐derived substrates into value‐added chemicals, coupled with hydrogen (H 2 ) evolution, offers a promising route for solar energy utilization and sustainable chemical production. However, achieving high efficiency and selectivity in such dual‐functional systems remains a challenge. Herein, the rational construction of a hierarchical Au/Zn 3 In 2 S 6 /Co 3 O 4 (Au/ZIS/Co 3 O 4 ) photocatalyst is reported for selective dehydrogenation of 5‐hydroxymethylfurfural (HMF) to 2,5‐diformylfuran (DFF), coupled with H 2 generation. The unique dual‐interfacial electric fields at the Au/ZIS and ZIS/Co 3 O 4 interfaces enable directional and spatially separated migration of photogenerated electrons and holes to Au and Co 3 O 4 , respectively. As a result, Au/ZIS/Co 3 O 4 achieves a remarkable H 2 evolution rate of 2012.4 µmol g −1 h −1 , with 67.2% of DFF yield and excellent recyclability, which is 7.7 times higher than blank Zn 3 In 2 S 6 (260.4 µmol g −1 h −1 ). This H 2 yield rate is the highest among reported photocatalysts for concurrent HMF valorization and H 2 production. Furthermore, the intrinsic quantum efficiency of the system is quantitatively evaluated for the first time by solving the radiative transfer equation in a tubular photoreactor. This work demonstrates a generalizable strategy for engineering redox‐site‐separated photocatalysts for biomass valorization and solar hydrogen production, offering valuable insights into the design principles of next‐generation photocatalytic systems for sustainable energy.
Li et al. (2025) studied this question.