Thiol-functionalized mesostructured silica with anhydrous compositions of (SiO(2))(1)(-)(x)()(LSiO(1.5))(x)(), where L is a mercaptopropyl group and x is the fraction of functionalized framework silicon centers, are effective trapping agents for the removal of mercuric(II) ions from water. In the present work, we investigate the mercury-binding mechanism for representative thiol-functionalized mesostructures by atomic pair distribution function (PDF) analysis of synchrotron X-ray powder diffraction data and by Raman spectroscopy. The mesostructures with wormhole framework structures and compositions corresponding to x = 0.30 and 0.50 were prepared by direct assembly methods in the presence of a structure-directing amine porogen. PDF analyses of five mercury-loaded compositions with Hg/S ratios of 0.50-1.30 provided evidence for the bridging of thiolate sulfur atoms to two metal ion centers and the formation of chain structures on the pore surfaces. We find no evidence for Hg-O bonds and can rule out oxygen coordination of the mercury at greater than the 10% level. The relative intensities of the PDF peaks corresponding to Hg-S and Hg-Hg atomic pairs indicate that the mercury centers cluster on the functionalized surfaces by virtue of thiolate bridging, regardless of the overall mercury loading. However, the Raman results indicate that the complexation of mercury centers by thiolate depends on the mercury loading. At low mercury loadings (Hg/S < or = 0.5), the dominant species is an electrically neutral complex in which mercury most likely is tetrahedrally coordinated to bridging thiolate ligands, as in Hg(SBu(t))(2). At higher loadings (Hg/S 1.0-1.3), mercury complex cations predominate, as evidenced by the presence of charge-balancing anions (nitrate) on the surface. This cationic form of bound mercury is assigned a linear coordination to two bridging thiolate ligands.

Atomic pair distribution functions (PDF) obtained from high energy x-ray synchrotron radiation, and x-ray absorption fine structure (XAFS) measurements, were performed on 18 closely spaced compositions of chalcogenide glasses (Ge x Se 1−x with 0.15 ≤ x ≤ 0.40), that span the range of the floppy to rigid phase transition in these glasses. Structural parameters such as PDF peak widths, Debye-Waller factors from EXAFS and the first sharp diffraction peak in S(Q), were extracted as a function of composition. These parameters evolve smoothly with composition, but there are no clear discontinuities or breaks in slope associated with the appearance of the intermediate phase (IP). Therefore, these measurements do not confirm a structural origin for the IP.

Alkali metals and their alloys can be protected from spontaneous reaction with dry air by intercalation (with subsequent heating) into the pores of silica gel (SG) at loadings up to 40 wt %. The resulting loose, black powders are convenient materials for chemical reduction of organic compounds and the production of clean hydrogen. The problem addressed in this paper is the nature of the reducing species present in these amorphous materials. The atomic pair distribution function (PDF), which considers both Bragg and diffuse scattering components, was used to examine their structures. Liquid Na-K alloys added to silica gel at room temperature (stage 0) or heated to 150 degrees C (stage I) as well as stage I Na-SG, retain the overall pattern of pure silica gel. Broad oscillations in the PDF show that added alkali metals remain in the pores as nanoscale metal clusters. 23Na MAS NMR studies confirm the presence of Na(0) and demonstrate that Na+ ions are formed as well. The relative amounts of Na(0) and Na(+) depend on both the overall metal loading and the average pore size. The results suggest that ionization occurs near or in the SiO2 walls, with neutral metal present in the larger cavities. The fate of the electrons released by ionization is uncertain, but they may add to the silica gel lattice, or form an "electride-like plasma" near the silica gel walls. A remaining mystery is why the stage I material does not show a melting endotherm of the encapsulated metal and does not react with dry oxygen. Na-SG when heated to 400 degrees C (stage II) yields a dual-phase reaction product that consists of Na(4)Si(4) and Na(2)SiO(3).