Spray-Drying-Based Surface-Enhanced Raman Spectroscopy: Effect of the Silver Nanoparticle Aggregate Size on the Enhancement of Raman Scattering

We report a spray-drying method to fabricate silver nanoparticle (AgNP) aggregates for application in surface-enhanced Raman spectroscopy (SERS). A custom-built system was used to fabricate AgNP aggregates of three sizes, 48, 86, and 218 nm, from drying droplets containing AgNPs atomized from an AgNP suspension. Sample solutions of Rhodamine B (RhB) at 10–6, 10–8, and 10–10 M concentrations were dropped onto the AgNP aggregates as probe molecules to examine the enhancement of the Raman signals of the RhB. The ordering of the analytical enhancement factors (AEFs) by aggregate size at a given RhB concentration was 86 nm > 218 nm > 48 nm. The AEFs of the 86 nm AgNP aggregates were higher than those of the 218-nm aggregates, although the 218-nm aggregates had more hot spots where Raman enhancement occurred. This finding was attributable to the deformation and damping of the electron cloud in the highly aggregated AgNPs, reducing the sensitivity for Raman enhancement. When RhB was premixed with the AgNP suspension prior to atomization, the AEFs at 10–8 M RhB rose ~100-fold compared to those in the earlier experiments (the post-dropping route). This significant enhancement was probably caused by the increased opportunity for the trapping of the probe molecules in the hot spots.

Photocatalytic Properties of Silver Nanospherical Arrays Driven by Surface Plasmons

Surface-enhanced Raman scattering (SERS) is a promising technique to study the plasma-driven photocatalytic reactions. Hemispherical alumina nanoarrays with a regular hexagonal arrangement are firstly prepared; then, silver hemispherical nanoarrays are synthesized on the surface of the arrays by silver evaporation. When a laser with a specific wavelength (633 nm) is irradiated on the silver nanoarrays, a large number of regularly arranged local surface plasmon enhancement regions (called “hot spots”) would be generated on its surface. After that, a layer of evenly distributed p-aminothiophenol (PATP) probe molecules was placed on the substrate and the photocatalytic reaction of PATP was driven by the local surface plasmon to form four 4′-di-mercaptoazobenzene (DMAB). Then, under the same experimental conditions, the later product was reversely reacted to form PATP molecule by the action of plasma in the presence of in situ sodium borohydride. SERS can be used to monitor the whole process of the photocatalytic reaction of PATP probe molecules driven by the plasma on the surface of the silver nanoarrays. This research achieves the drawing and erasing of molecular graphics in the micro- and nano-scales, as well as information encryption, reading, and erasing that have strong application value.

The Properties of Cu Ions in Zeolites CuY Studied by IR Spectroscopy

The properties of both Cu2+ and Cu+ ions in zeolite CuY were followed with NO and CO as probe molecules. Cu2+ was found to be located in SII, SII*, and SIII sites, whereas Cu+ was found in SII and SII* sites. The fine analysis of the spectra of Cu2+-NO and Cu+-CO adducts suggests that both in SII and in SII* sites two kinds of Cu cations exist. They differ in the positive charge, which may be related to the varying numbers of AlO4− in close proximity. The experiments of NO and CO adsorption and desorption evidenced that both Cu2+ and Cu+ sites of highest positive charge bind probe molecules most strongly but activate them to a lesser extent than the Cu sites of lowest positive charge. The experiments of reduction with hydrogen evidenced that the Cu ions of higher positive charge are first reduced by hydrogen. On the other hand, Cu sites of the lowest positive charge are first oxidized by oxygen. The experiments with CuNaY zeolites of various Cu contents suggest that the first introduced Cu (at low Cu contents) created Cu+, which was the most neutralized by framework oxygens. Such Cu cations are the most stabilized by framework oxygens.