Synergistic adsorption of heavy metal ions and organic pollutants by supramolecular polysaccharide composite materials from cellulose, chitosan and crown ether.

We have developed a simple one-step method to synthesize novel supramolecular polysaccharide composites from cellulose (CEL), chitosan (CS) and benzo-15-crown 5 (B15C5). Butylmethylimidazolium chloride [BMIm(+)Cl(-)], an ionic liquid (IL), was used as a sole solvent for dissolution and preparation of the composites. Since majority of [BMIm(+)Cl(-)] used was recovered for reuse, the method is recyclable. The [CEL/CS+B15C5] composites obtained retain properties of their components, namely superior mechanical strength (from CEL), excellent adsorption capability for heavy metal ions and organic pollutants (from B15C5 and CS). More importantly, the [CEL/CS+B15C5] composites exhibit truly supramolecular properties. By itself CS, CEL and B15C5 can effectively adsorb Cd(2+), Zn(2+) and 2,4,5-trichlorophenol. However, adsorption capability of the composite was substantially and synergistically enhanced by adding B15C5 to either CEL and/or CS. That is, the adsorption capacity (qe values) for Cd(2+) and Zn(2+) by [CS+B15C5], [CEL+B15C5] and [CEL+CS+B15C5] composites are much higher than combined qe values of individual CS, CEL and B15C5 composites. It seems that B15C5 synergistically interact with CS (or CEL) to form more stable complexes with Cd(2+) (or Zn(2+)), and as a consequence, the [CS+B15C5] (or the [CEL+B15C5]) composite can adsorb relatively larger amount Cd(2+) (or Zn(2+)). Moreover, the pollutants adsorbed on the composites can be quantitatively desorbed to enable the [CS+CEL+B15C5] composites to be reused with similar adsorption efficiency.