Facile preparation of perylene imide based supramolecular structure with strong internal electric-field for enhancing photocatalytic nitrogen fixation

Rational regulating supramolecular structure with built-in electric field is a promising tactic to improve the separation of charge carriers and photocatalytic nitrogen fixation efficiency. However, those synthetic procedures are complicated, time-consuming, and low-scale preparation. Here, we reported a simple tactic to prepare perylene diimide (PDI)-triazine-based supramolecular using the solution-dispersed supramolecular self-assembly method. The PDI-triazine-based supramolecular obtains an outstanding nitrogen fixation rate and near IR yield in pure water, which was about 10 times higher than that of pristine PDI. The DFT calculation and experiment reveal that embeds triazine units reasonably regulated the HOMO and LOMO band and the absorption properties, which guaranteed the PDIMA enable to absorb the near IR light and activate the N2 molecule. Moreover, the adjustable face-to-face arrangement of π–π stacking and intrinsic molecular dipole is conducive to the construction of built-in electric field, resulting in high carrier separation efficiency. This study provides a facile strategy to incorporate foreign groups for enhancing photocatalytic efficiency over organic-based supramolecular.