Dendritic Anion Hosts: Perchlorate Uptake by G5-NH_2 Poly(propyleneimine) Dendrimer in Water and Model Electrolyte Solutions

摘要

Perchlorate (CIO_4~- ) has emerged as a major groundwater and surface water contaminant in the United States. Ion exchange (Ⅸ) is the most widely used technology for treating water containing lower concentrations of perchlorate (< 100 ppb). However, a major drawback of Ⅸ is the need for frequent regeneration or disposal of the perchlorate-laden resins. As a first step toward the development of high-capacity, selective and recyclable dendritic ligands for the recovery of perchlorate from aqueous solutions by dendrimer filtration, we tested the hypothesis that dendrimers with hydrophobic cavities and positively charged internal groups should selectively bind CIO_4~- over more hydrophilic anions such as Cl~-, NO_3~-, SO_4~(2-), and HCO_3~-. We measured the uptake of ClO_4~- by the fifth generation (G5-NH_2) poly(propyleneimine) (PPI) dendrimer with a diaminobutane core and terminal NH_2 groups in deonized water and model electrolyte solutions as a function of (ⅰ) anion-dendrimer loading, (ⅱ) solution pH, (ⅲ) background electrolyte concentration, and (ⅳ) reaction time. The CIO_4~- binding capacity of this dendrimer is comparable to those of perchlorate-selective Ⅸ resins. However, its CIO_4~- binding kinetics is faster and reaches equilibrium in ～1 h. Note also that only a high pH (～ 9.0) aqueous solution is needed to release more than 90% of the bound CIO_4~- anions by deprotonation of the dendrimer tertiary amine groups. The overall results of this study suggest that dendritic macromolecules such as the G5-PPI NH_2 dendrimer provide ideal building blocks for the development of high-capacity, selective and recyclable ligands for the recovery of anions such as perchlorate from aqueous solutions by dendrimer enhanced filtration.