Spatially Decoupled Redox Pathways in 2D/2D g-C3N4/ZnIn2S4 Enable Highly Selective Aerobic Photooxidation of Biomass

• • Achieved HMF-to-DFF photo-conversion rate of 1517.5 μmol g−1 h−1 with 99.4% selectivity under ambient air, outperforming state-of-the-art catalysts and enabling efficient biomass valorization. • • Spatial decoupling in 2D/2D g-C3N4/ZnIn2S4 selectively generates ·O2− while suppressing ·OH, preventing over-oxidation and enhancing product selectivity. • • KPFM and DFT confirm directed electric field drives selective O2 activation at ZnIn2S4 domains, while g-C3N4 anchors HMF via –OH interactions, optimizing C–H cleavage. • • Catalyst maintains durable cycling performance, indicating potential for scalable, sustainable chemical manufacturing under mild conditions.