Bioinspired Mortise‐and‐Tenon Stacking Supramolecular Engineering for Efficient Carrier Separation in S‐Scheme Heterojunctions
Bing Wang, Yao Liu, Yuzhen Zhao, Enzhou Liu, Zhuo Li, Zongcheng Miao
Abstract
Abstract Inspired by the mechanical interlocking principles of traditional Chinese mortise‐and‐tenon structures, a 3D gradient supramolecular network is developed through oriented self‐assembly of subphthalocyanine (SubPc‐0) arrays on La‐doped Ag 3 PO 4 (La 0.01 Ag 2.99 PO 4 ). This bioinspired design synergistically combines π‐orbital topological extension with dynamic B–La coordination bonds to construct an S‐scheme heterojunction with dual‐phase charge modulation capability. Mechanistic studies reveal that La 3+ doping induces anisotropic electron delocalization for directional bulk charge transfer, while S‐scheme interfacial coupling establishes ultrafast (<10 ps) atomic‐scale charge transport channels through orbital hybridization. The optimized SubPc‐0/La 0.01 Ag 2.99 PO 4 system demonstrates 2.2‐ and 2.1‐fold improvements in tetracycline and oxytetracycline degradation efficiencies, respectively, with 94% activity retention after five cycles. Advanced characterization techniques including femtosecond transient absorption spectroscopy (fs‐TAS) and Kelvin probe force microscopy (KPFM), combined with theoretical calculations, elucidated the intricate photocatalytic mechanism and charge transfer pathways. This work delivers an effective design strategy and mechanistic insights for the stacking engineering of S‐scheme photocatalytic materials.