Uncovering the interaction between photocatalyst and reaction substrate as well as subsequent electron transfer process is critical to achieve high-performance photodegradation of pollutants. Herein, based on the reduced density gradient (RDG) method, we visualize the simulation of the π-π interactions between photocatalyst (g-C3N4) and pollutant molecule (flumequine, FLU). Results revealed that π-π interactions between g-C3N4 and FLU favor electrons delivery, resulting in enhanced charge separation efficiency and direct hole oxidation of FLU. Moreover, it is found that the charge transfer rate is determined by the valence band (VB) level of g-C3N4 and EHOMO of FLU, of which the deeper VB position of g-C3N4 favors faster charge transfer, leading to further enhancement in photocatalytic degradation rate of FLU. Additionally, the possible degradation pathways of FLU were proposed by theoretical calculation and the determined intermediates. Our work afforded a new insight into pollutants degradation and the rational design of highly efficient photocatalysts.
Keywords: Interface interaction; Molecular level; Structure-function relationship; π-π interactions.
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