Charge-assisted hydrogen bond (CAHB) is a key mechanism that affects the environmental behavior of pharmaceutical pollutants (PCs). However, the strength and stability of various CAHBs, and their effects on the co-sorption behavior of PCs are still unclear. Herein, DFT calculation with different solvent models including two implicit solvent model (PCM and SMD), and one explicit solvent model (ESM) were applied in this study, to investigate the effects of different CAHBs on the sorption and co-sorption behavior of four PCs (e.g., clofibric acid, p-aminobenzoic acid, acetaminophen, and sulfamerazine) on three model carbonaceous materials. First, the appearance of new peaks in the very low field of 1H NMR, and the blue shift of OH and NH2 peaks in FTIR indicated that CAHBs were indeed formed between PCs and carbonaceous materials. Next, according to the principal component analysis and correlation analysis of parameters (e.g., ΔEads, bond length, bond angle, Egap, and ΔG) of these CAHBs calculated by the DFT with different solvent models, the results showed that SMD is the optimal model for calculating the strength and stability of CAHBs by DFT, and the strength and stability of CAHBs formed between PCs and carbonaceous materials in this study were in the order of homonuclear [O⋯H⋯O]− CAHB > heteronuclear [O⋯HN]−/[N⋯HO]+ type of CAHB > homonuclear [N⋯H⋯N]+. Also, the co-sorption behavior of different PCs co-existing in binary systems further confirmed that, all above types of CAHBs formed between PCs and carbonaceous materials can produce obvious competition effect on the co-existing PCs that only OHB formed between them. This study not only reveals the environmental behavior of co-existing PCs, but also provides a theoretical basis for the design of obligate sorption materials for PCs in the natural environment.

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