DFT Predirected Molecular Engineering Design of Donor‐Acceptor Structured g‐C3N4 for Efficient Photocatalytic Tetracycline Abatement

Abstract The photocatalytic environmental decontamination ability of carbon nitride (g‐C3N4, CN) typically suffers from their inherent structural defects, causing rapid recombination of photogenerated carriers. Conjugating CN with tailored donor–acceptor (D–A) units to counteract this problem through electronic restructuring becomes a feasible strategy, where confirmation by density functional theory (DFT) calculations becomes indispensable. Herein, DFT is employed to predirect the copolymerization modification of CN by benzene derivatives, screening benzaldehyde as the optimal electron‐donating candidate for the construction of reoriented intramolecular charge transfer path. Experimental characterization and testing corroborate the formation of a narrowed bandgap as well as high photoinduced carrier separation. Consequently, the optimal BzCN‐2 exhibited superior photocatalytic capacity in application for tetracycline hydrochloride degradation, with 3.73 times higher than that of CN. Besides, the BzCN‐2‐based photocatalytic system is determined to have a toxicity‐mitigating effect on TC removal via T.E.S.T and prefers the removal of dissociable TC2− species under partial alkalinity. This work provides insight into DFT guidance for the design of D–A conjugated polymer and its application scenarios in photocatalytic decontamination.