Development and Upscaling of SiO2@TiO2 Core-Shell Nanoparticles for Methylene Blue Removal.

SiO2@TiO2 core-shell nanoparticles were successfully synthesized via a simple, reproducible, and low-cost method and tested for methylene blue adsorption and UV photodegradation, with a view to their application in wastewater treatment. The monodisperse SiO2 core was obtained by the classical Stöber method and then coated with a thin layer of TiO2, followed by calcination or hydrothermal treatments. The properties of SiO2@TiO2 core-shell NPs resulted from the synergy between the photocatalytic properties of TiO2 and the adsorptive properties of SiO2. The synthesized NPs were characterized using FT-IR spectroscopy, HR-TEM, FE-SEM, and EDS. Zeta potential, specific surface area, and porosity were also determined. The results show that the synthesized SiO2@TiO2 NPs that are hydrothermally treated have similar behaviors and properties regardless of the hydrothermal treatment type and synthesis scale and better performance compared to the SiO2@TiO2 calcined and TiO2 reference samples. The generation of reactive species was determined by EPR, and the photocatalytic activity was evaluated by the methylene blue (MB) removal in aqueous solution under UV light. Hydrothermally treated SiO2@TiO2 showed the highest adsorption capacity and photocatalytic removal of almost 100% of MB after 15 min in UV light, 55 and 89% higher compared to SiO2 and TiO2 reference samples, respectively, while the SiO2@TiO2 calcined sample showed 80%. It was also observed that the SiO2-containing samples showed a considerable adsorption capacity compared to the TiO2 reference sample, which improved the MB removal. These results demonstrate the efficient synergy effect between SiO2 and TiO2, which enhances both the adsorption and photocatalytic properties of the nanomaterial. A possible photocatalytic mechanism was also proposed. Also noteworthy is that the performance of the upscaled HT1 sample was similar to one of the lab-scale synthesized samples, demonstrating the potentiality of this synthesis methodology in producing candidate nanomaterials for the removal of contaminants from wastewater.

A General Route for Growing Metal Sulfides onto Graphene Oxide and Exfoliated Graphite Oxide.

Graphene-based materials are elective materials for a number of technologies due to their unique properties. Also, semiconductor nanocrystals have been extensively explored due to their size-dependent properties that make them useful for several applications. By coupling both types of materials, new applications are envisaged that explore the synergistic properties in such hybrid nanostructures. This research reports a general wet chemistry method to prepare graphene oxide (GO) sheets decorated with nanophases of semiconductor metal sulfides. This method allows the in situ growth of metal sulfides onto GO by using metal dialkyldithiocarbamate complexes as single-molecule precursors. In particular, the role of GO as heterogeneous substrate for the growth of semiconductor nanocrystals was investigated by using Raman spectroscopic and imaging methods. The method was further extended to other graphene-based materials, which are easily prepared in a larger scale, such as exfoliated graphite oxide (EGO).

Functionalized magnetite particles for adsorption of colloidal noble metal nanoparticles.

Magnetite (inverse spinel type) particles have been surface-modified with siliceous shells enriched in dithiocarbamate groups. The deposition of colloidal noble metal nanoparticles (Au, Ag, Pt, Pd) onto the modified magnetites can be performed by treating the respective hydrosols with the magnetic sorbents, thus allowing their uptake from water under a magnetic gradient. In particular, for Au colloids, these magnetic particles are very efficient sorbents that we ascribe to the strong affinity of sulfur-containing groups at the magnetite surfaces for this metal. Considering the extensive use of Au colloids in laboratorial and industrial contexts, the approach described here might have an impact on the development of nanotechnologies to recover this precious metal. En route to these findings, we varied several operational parameters in order to investigate this strategy as a new bottom-up assembly method for producing plasmonic-magnetic nanoassemblies.