Montmorillonite (Mt) is proposed as a promising adsorbent for removing contaminants from water, yet it is unclear whether and how the layer charge density (LCD) of Mt. affects its hydration properties, especially for the capturing performance of anions by polyelectrolyte modified Mt. Here, the feasibility and performance of perchlorate uptake by poly-(diallydimethylammonium chloride) (PDDA) functionalized Mt. (PDDA-Mtx) with different LCD were investigated. PDDA species were loaded via partial intercalation or adsorption on the surface/end sites of Mt. The CEC of Ca-Mtx increased with increasing LCD, while on the contrary for colloidal valence. The perchlorate uptake by Ca-Mtx can be significantly improved by introducing PDDA species. As expected, the PDDA-Mt0.3 showed superior perchlorate capture of up to 0.80 mmol/g due to the relatively high positive zeta potential and loading of un-ionized PDDA. The perchlorate uptake by PDDA-Mtx still maintained largely despite a slight decrease in the presence of co-competing anions NO-3, SO2–4 and PO3–4. The capture behaviors were well characterized by the pseudo-second-order and Langmuir isotherm models, and the natures of spontaneous and endothermic were demonstrated by thermodynamic analysis. Anion exchange and electrostatic were the dominant ways in which perchlorate was captured onto PDDA-Mtx.
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