3-APTES on Dendritic Fibrous Mesoporous Silica Nanoparticles for the pH-Controlled Release of Corrosion Inhibitors.

Mesoporous silica nanoparticles (MSNPs) are currently used in different fields like catalysis, nanomedicine, and conservation science, taking advantage of their high surface area. Here, we synthesized and functionalized mesoporous dendritic fibrous nanoparticles to realize a smart delivery system of protective agents for metals. Different MSNPs were obtained via the microemulsion method followed by a hydrothermal or refluxing treatment at different w/o ratios, times, and temperatures. Dendritic spherical silica nanoparticles with specific features such as an appropriate size (450 nm), a very large surface area (600 m2 g-1), and a high yield synthesis (86%) were selected for surface modification. The fiber surface of the selected MSNPs was functionalized with 3-aminopropyl triethoxysilane (3-APTES). 3-APTES works as a pH-driven "nanogate", suppressing the immediate leakage of the total guest molecule load and modulating the release as a function of pH conditions. Surface-modified MSNPs were tested as a reservoir of the most diffused corrosion inhibitors: Mercaptobenzothiazole (MBT) and 1H-Benzotriazole (BTA); their release properties were studied in solutions with pH = 4 and 7. Functionalized and non-functionalized MSNPs showed a good loading efficiency of guest molecules (34-64%) and a pH-dependent release of the corrosion inhibitors on a timescale of several hours.

Oscillatory Behaviour of Ni Supported on ZrO2 in the Catalytic Partial Oxidation of Methane as Determined by Activation Procedure.

Ni/ZrO2 catalysts, active and selective for the catalytic partial oxidation of methane to syngas (CH4-CPO), were prepared by the dry impregnation of zirconium oxyhydroxide (Zhy) or monoclinic ZrO2 (Zm), calcination at 1173 K and activation by different procedures: oxidation-reduction (ox-red) or direct reduction (red). The characterization included XRD, FESEM, in situ FTIR and Raman spectroscopies, TPR, and specific surface area measurements. Catalytic activity experiments were carried out in a flow apparatus with a mixture of CH4:O2 = 2:1 in a short contact time. Compared to Zm, Zhy favoured the formation of smaller NiO particles, implying a higher number of Ni sites strongly interacting with the support. In all the activated Ni/ZrO2 catalysts, the Ni-ZrO2 interaction was strong enough to limit Ni aggregation during the catalytic runs. The catalytic activity depended on the activation procedures; the ox-red treatment yielded very active and stable catalysts, whereas the red treatment yielded catalysts with oscillating activity, ascribed to the formation of Niδ+ carbide-like species. The results suggested that Ni dispersion was not the main factor affecting the activity, and that active sites for CH4-CPO could be Ni species at the boundary of the metal particles in a specific configuration and nuclearity.