Adsorption of sulfamethoxazole and sulfadiazine on phosphorus-containing stalk cellulose under different water pH...

To improve the high-value application of corn stalk, phosphorus-containing stalk cellulose (PFC) was prepared, characterized, and utilized for the adsorption of sulfamethoxazole (SMZ) and sulfadiazine (SD), with maximum adsorption capacities of 1.385 and 2.527 mg/g at pH 7. As expected, the adsorption efficiency of PFC was strongly affected by pH, and the preferential adsorption order of SMZ^- (SD⁰) > SMZ⁰ (SD^-) > SMZ⁺ (SD⁺) was obtained from the experimental results and due to the charges of PFC and the SMZ and SD species. Furthermore, these results were qualitatively linked to the adsorption mechanism, e.g., π⁺-π electron donor-acceptor (EDA), anion-π bond electrostatic, and hydrophobic interactions. In particular, the adsorption mechanism was further characterized in terms of structure and analyzed systematically using density functional theory (DFT), frontier orbital theory (FOT), and molecular dynamics (MD) simulation, with the aim to explain the theoretical calculation and experimental results. As a result, the highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) orbitals revealed the key role of the rings and functional groups of PFC and SMZ (or SD) and validated the optimized structures of PFC⁺ sulfonamides (SAs)⁺, PFC^- SAs⁰, and PFC^- SAs^-, in which their binding energy values, energy gaps, and relevant molecular lengths determined their stability. Additionally, the van der Waals (vdW) energy confirmed the effect of various interactions on adsorption.