Defective Potassium Poly(Heptazine Imide) Preventing Spin Delocalization and Hole Transfer Deactivation for Efficient Solar Energy Conversion and Storage

Abstract Anti‐site defective potassium poly(heptazine imide) (KPHI) with the central nitrogen atoms partially replaced by graphitic carbon atoms in the flawed heptazine rings is prepared by direct ionothermal treatment of the rationally designed supramolecular complex in KSCN salt molten. Compared to the KPHIs without the anti‐site defect, the anti‐site defective KPHI demonstrates significantly improved photocatalytic and dark photocatalytic performances for H₂ evolution reaction (HER). In the presence of the hole scavenger, the anti‐site defective KPHI exhibits superior photocatalytic stability for HER lasting 20 h, whereas the deactivation is observed from the ordinary KHPIs after 3 h HER. Moreover, the H₂ yield in the dark by the stored photoelectrons in the anti‐site defective KPHI increases by more than an order of magnitude. Density functional theory calculations reveal that the anti‐site defective unit in KPHI not only prevents spin delocalization but also inhibits the deactivation of hole transfer, which are beneficial to photoelectron storage and photocatalytic activity. The findings in this study provide insight into the photophysical and catalytic properties of KPHI, which conclude a strategy to improve the performances for solar energy conversion and storage by incorporating intrinsic anti‐site defects in KPHI.