Enhanced selective adsorption of benzotriazole onto nanosized zeolitic imidazolate frameworks confined in polystyrene anion exchanger
A new nanocomposite adsorbent ZIF-67/D201, in which nanocrystalline ZIF-67 were immobilized inside the networking pores of a commercial polystyrene anion exchanger D201 by an alternate deposition method, with high capacity and enhanced selective affinity toward benzotriazole (BTA) was fabricated and characterized. ZIF-67/D201 demonstrated precise selective adsorption of BTA when benzimidazole (BMA), with very similar chemical structure to BTA, coexisted. After the uptake of BTA, ZIF-67/D201 could be regenerated for repeated use with slight capacity loss. According to kinetics data, two diffusion steps driven by electrostatic attraction were found prior to adsorption equilibrium: a fast diffusion of the contaminant into mesopores of D201 and then a relatively slow diffusion into micropores of ZIF-67. The underlying mechanism for the enhanced selective adsorption was revealed by spectral analysis and density functional theory (DFT) calculations. Three sorts of interactions (coordination, electrostatic attraction and π-π interaction) contributed to the fixing of contaminants. Among them, coordination was the predominant effect. For each sort of interaction, the binding energy of adsorbent-BTA was always larger than that of adsorbent-BMA, which was the intrinsic reason of the high selectivity in molecular level. The above results provided a strategy for precise separation of components with similar structures in water.
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