Design and Synthesis of Selective Mesoporous Anion Traps

Abstract

Arsenic contamination of groundwater has recently commanded widespread public attention. Under many conditions, arsenic, and certain other environmentally relevant toxic metals such as chromium, exist in nature as oxyanions. Selective binding of anions is one of the most challenging problems in chemistry, biology, and materials and environmental science. In this paper we report the synthesis and use of metal-chelated ligands immobilized on mesoporous silica as novel anion binding materials. Nearly complete removal of arsenate and chromate has been achieved in the presence of competing anions for solutions containing more than 100 mg/L (ppm) toxic metal anions under a variety of conditions. Anion loading of more than 120 mg (anion)/g of adsorption materials is observed. A binding mechanism is also proposed on the basis of computer modeling. First, Cu(II) ions are bonded to ethylenediamine (EDA) ligands to form octahedral complexes on the surface of the mesoporous silica. This gives rise to positively charged hosts with 3-fold symmetry that match the geometry of tetrahedral anions. The anion binding involves initial electrosteric coordination, followed by displacement of one ligand and direct binding with the Cu(II) center.