Intermolecular H-bonding and tetrameric π-stacking enable dual "mortise-and-tenon" jointed S-scheme supramolecular arrays for efficient carrier separation

The rational design of stable charge-transfer pathways remains a critical challenge in advancing S-scheme photocatalytic systems. Herein, we demonstrate a hydrogen-bond-engineered dual mortise-and-tenon supramolecular architecture using precisely tailored H 12 SubPcB-OCONapOH (SubPc-5) molecules, which synergistically enhance interfacial carrier dynamics and structural robustness. The SubPc-5/TiO 2 heterojunction, constructed through π-π-directed self-assembly, achieves exceptional photocatalytic degradation of oxytetracycline (90%) and tetracycline (99%) within 180   minutes, outperforming pristine TiO 2 by 3–4.5-fold in reaction kinetics. Multimodal mechanistic investigations, including in situ light-irradiated Kelvin probe analysis, synchronous irradiation X-ray photoelectron spectroscopy (SI-XPS), and density functional theory (DFT) calculations, unambiguously verify the S-scheme charge transfer between TiO 2 and SubPc-5. Theoretical investigations reveal that O 2 molecules adsorbed at the O-site on the TiO 2 (101) surface more efficiently capture photogenerated electrons compared to the Ti-site. This work pioneers a supramolecular engineering strategy for constructing mechanically stable and electronically efficient photocatalytic systems, highlighting the transformative potential of mortise-and-tenon nanostructures in environmental remediation applications.