XAS study of mercury(II) ions trapped in mercaptan - Functionalized mesostructured silicate with a wormhole framework structure

Directly assembled wormhole mesostructures with high level functionalized mercaptan (MP-HMS) have been shown to be effective mercury(II) (Hg2+) trapping agents. Sorption of Hg2+ onto MP-HMS was investigated using X-ray absorption spectroscopy (XAS) to identify the structural coordination of the adsorbed Hg. Samples with different fractions of mercaptan functionalized groups (i.e., x = 0.1 and 0.5) with various Hg/S molar ratios ranging from 0.05 to 1.4 were investigated. XAS analysis indicates that adsorbed Hg first coordination shell is best fitted with an Hg-O path and an Hg-S path. The Hg-S atomic distance (RHg-S) remained relatively constant while the Hg-S coordination numbers (CN) decreased as Hg/S loading increased. For the Hg-0 path, both the CN and the RHg-O increased with increasing Hg loading. XAS results suggest that at low Hg loadings, adsorbed Hg2+ forms mostly monodentate sulfur complexes (-S-Hg-OH) with the sulfur functional groups on the MP-HMS surfaces. At high Hg loadings, the Hg coordination environment is consistent with the formation of a double-layer structure of Hg attached to sulfur binding sites (-S-Hg-O-Hg-OH).