Through‐Space Electron Coupling in Nonaromatic Architectures Drives Solar Hydrogen Production

The rational design of next-generation photocatalytic materials capable of simultaneously addressing sustainability challenges and performance demands represents a critical frontier in photocatalysis research. Herein, these finding are reported that nonaromatic biomass-derived architectures have exceptional visible-to-near-infraredphotocatalytic activity for hydrogen evolution via a novel 3D through-space conjugation (TSC) mechanism, which leads to a transformative strategy for sustainable hydrogen production. It is identified that the oxygen-mediated 2p orbital hybridization in these biomass-derived materials constitutes semiconductor-like band structures with exceptionally broad band light absorption capabilities. Moreover, the inherent electronegativity gradient among carbon, hydrogen, and oxygen atoms creates an asymmetric charge distribution, generating substantial molecular dipole moments (>10 Debye) that leads to enhanced charge separation. The optimized materials achieve record-high apparent quantum yields of 44.63% (420 nm) and 1.58% (800 nm) for hydrogen production, rivaling state-of-the-art photocatalysts. This revealed TSC mechanism fundamentally redefines the design paradigm for organic photocatalysts, creating a sustainable materials platform that concurrently enables biomass valorization and efficient solar fuel generation. These findings represent a conceptual breakthrough in the photocatalyst design, offering a vast opportunity for advancing next-generation solar fuel technologies.