TiO2 Nanoparticles with Adjustable Phase Composition Prepared by an Inverse Microemulsion Method: Physicochemical Characterization and Photocatalytic Properties.

Titania nanoparticles (NPs) find wide application in photocatalysis, photovoltaics, gas sensing, lithium batteries, etc. One of the most important synthetic challenges is maintaining control over the polymorph composition of the prepared nanomaterial. In the present work, TiO2 NPs corresponding to anatase, rutile, or an anatase/rutile/brookite mixture were obtained at 80 °C by an inverse microemulsion method in a ternary system of water/cetyltrimethylammonium bromide/1-hexanol in a weight ratio of 17:28:55. The only synthesis variables were the preparation of the aqueous component and the nature of the Ti precursor (Ti(IV) ethoxide, isopropoxide, butoxide, or chloride). The materials were characterized with X-ray diffraction, scanning/transmission electron microscopy, N2 adsorption-desorption isotherms, FTIR and Raman vibrational spectroscopies, and diffuse reflectance spectroscopy. The synthesis products differed significantly not only in phase composition, but also in crystallinity, textural properties, and adsorption properties towards water. All TiO2 NPs were active in the photocatalytic decomposition of rhodamine B, a model dye pollutant of wastewater streams. The mixed-phase anatase/rutile/brookite nanopowders obtained from alkoxy precursors showed the best photocatalytic performance, comparable to or better than the P25 reference. The exceptionally high photoactivity was attributed to the advantageous electronic effects known to accompany multiphase titania composition, namely high specific surface area and strong surface hydration. Among the single-phase materials, anatase samples showed better photoactivity than rutile ones, and this effect was associated, primarily, with the much higher specific surface area of anatase photocatalysts.

Composites of Montmorillonite and Titania Nanoparticles Prepared by Inverse Microemulsion Method: Physico-Chemical Characterization.

TiO2/montmorillonite composites were synthesized using inverse micellar route for the preparation of titania nanoparticles (4-6 nm diameter) in 1-hexanol and for the dispersion of one of the clay components. Two series of composites were obtained: one derived from cetyltrimethylammonium organomontmorillonite (CTA-Mt), exfoliated in 1-hexanol, and the other from sodium form of montmorillonite (Na-Mt) dispersed by formation of an inverse microemulsion in 1-hexanol. The TiO2 content ranged from 16 to 64 wt.%. The composites were characterized with X-ray diffraction, scanning/transmission electron microscopy/energy dispersive X-ray spectroscopy, thermal analysis, and N2 adsorption-desorption isotherms. The Na-Mt-derived component was shown to undergo transformation to CTA-Mt, as indicated by basal spacing of 17.5 nm, due to the interaction with the CTABr surfactant in inverse microemulsion. It was also better dispersed and intermixed with TiO2 nanoparticles. As a result, the TiO2/Na-Mt series displayed superior textural properties, with specific surface area up to 256 m2g-1 and pore volume up to 0.247 cm3g-1 compared with 208 m2g-1 and 0.231 cm3g-1, respectively, for the TiO2/CTA-Mt counterpart. Members of both series were uniformly mesoporous, with the dominant pore size around 5 nm, i.e., comparable with the dimensions of titania nanoparticles. The advantage of the adopted synthesis method is discussed in the context of other preparative procedures used for manufacturing of titania-clay composites.

Polymerization of aniline hydrochloride in reverse of microemulsion by batch and semicontinuous process using ionic and nonionic surfactants.

The polymerization of aniline hydrochloride by inverse microemulsion in a batch process and the semicontinuous process was studied as a function of the surfactant ionic and nonionic. Polymerizations were carried out at 60°C for 4 h with a yield polymer of circa 67 and 27% wt. for ionic and nonionic surfactants. The conductivity of synthesized polyaniline by the semicontinuous process is higher up to three orders of magnitude than that of the batch process for both surfactants. The calculating degree of oxidation by UV-Vis showed the relative intensities of the quinoid to benzenoid unit around one. The morphology was determined by Scanning Electron Microscopy (SEM) and observed that the formation of the different morphologies is due to the self-assembly behavior of surfactant. The diameter z-average particle size (Dz) was studied by Transmission Electron Microscopy (TEM), which determined that the diameter particle in a semicontinuous state is larger than the one produced in a batch; this is due to the control of monomer addition in the system. These findings suggest that the polymerization process and the type of surfactant influence the properties of polyaniline.

Effect of water-oil ratio on the photocatalytic performance of visible light-active BiVO4 nanoparticles prepared by inverse microemulsion-calcination method.

Nowadays, nano-photocatalysts (NPs) have become the research focus in the field of photocatalysis due to their excellent photocatalytic activity, and microemulsion is an effective method to prepare high-efficiency nano-photocatalysts. Here, BiVO4 NPs with high efficiency under visible light were prepared by a combination of reverse microemulsion method and calcination method. XRD, SEM, TEM, XPS, DRS, PL, BET and other characterization tests were used to comprehensively explore the influence of water-oil ratio on the physicochemical properties of the catalysts. The results show that BiVO4 NPs of monoclinic scheelite with high crystallization degree can be obtained by this method. The microscopic morphology, specific surface area and total pore volume of BiVO4 NPs are significantly affected by the water-oil ratio. It is difficult to obtain BiVO4 NPs with small particle size and uniform dispersion under the condition of too low or too high water-oil ratio. Meanwhile, the photogenerated carrier recombination efficiency of the catalyst is significantly improved, thus reducing the photocatalytic activity of the catalyst. Strikingly, the BiVO4 NPs obtained under the condition of water-oil ratio is 20 exhibited well-dispersed nanospheres with diameters ranging from 80 to 100 nm. It has the highest photocatalytic activity due to its high crystallinity, large specific surface area and total pore volume and relatively low photogenerated carrier recombination efficiency. Under visible light irradiation, the degradation efficiency of RhB can reach 97.69% in 100 min, and the rate constant is 0.03253 min-1.

Polyamidoamine Dendrimer Microgels: Hierarchical Arrangement of Dendrimers into Micrometer Domains with Expanded Structural Features for Programmable Drug Delivery and Release.

In this paper, we report on the fabrication of micron-sized dendrimer hydrogels (µDHs) using the water-in-oil (w/o) inverse microemulsion method coupled with the highly efficient aza-Michael addition. EDA core polyamidoamine (PAMAM) dendrimer G5 (10 w%) and polyethylene glycol diacrylate (PEG-DA, M n = 575 g/mol) (the molar ratio of amine/acrylate = 1/1) were dissolved in the water phase and added to hexane in the presence of surfactants span 80/tween 80 (5/1, w/w) (volume ratio of hexane to surfactants: 70:1) to form w/o microemulsions, in which PAMAM G5 cross-links with PEG-DA via the aza-Michael addition reaction. The resulting microgels are within 3-5 µm with relatively narrow size distribution. µDHs are pH-responsive degradable. They show good cytocompatibility and do not cause acute toxicity in vivo. Furthermore, they can realize a high loading of the hydrophobic drug CPT and enter the cells in the form of particles. The CPT and CPT/dendrimer complex can be slowly released following the zero-order release kinetics. Taken together, µDHs possessing hierarchically ordered dendrimers in micron domains represent a new class of microparticles with expanded structural features for programmable drug delivery and release.

Composites of Laponite and Cu⁻Mn Hopcalite-Related Mixed Oxides Prepared from Inverse Microemulsions as Catalysts for Total Oxidation of Toluene.

Composites of Laponite and Cu⁻Mn hopcalite-related mixed oxides, prepared from hydrotalcite-like (Htlc) precursors obtained in inverse microemulsions, were synthesized and characterized with XRF, XRD, SEM, TEM, H2 temperature-programmed reduction (TPR), and N2 adsorption/desorption at -196 °C. The Htlc precursors were precipitated either with NaOH or tetrabutylammonium hydroxide (TBAOH). Al was used as an element facilitating Htlc structure formation, and Ce and/or Zr were added as promoters. The composites calcined at 600 °C are mesoporous structures with similar textural characteristics. The copper⁻manganite spinel phases formed from the TBAOH-precipitated precursors are less crystalline and more susceptible to reduction than the counterparts obtained from the precursors synthesized with NaOH. The Cu⁻Mn-based composites are active in the combustion of toluene, and their performance improves further upon the addition of promoters in the following order: Ce < Zr < Zr + Ce. The composites whose active phases are prepared with TBAOH are more active than their counterparts obtained with the use of the precursors precipitated with NaOH, due to the better reducibility of the less crystalline mixed oxide active phase.

Synthesis and characterization of Schiff base contained dextran microgels in water-in-oil inverse microemulsion.

Polysaccharide-based microgels with high water content, excellent biocompatibility and controllable particle size have been widely studied as ideal candidates for drug release and delivery. In this study, microgels based on dextran were developed via the Schiff base formation between aldehyded dextran and ethylenediamine in a water-in-oil (W/O) microemulsion. Particle size of the resulted microgel was controllable between 800 and 1100nm by modulating the amount of the employed co-surfactants (Span 80/Tween 80). Furthermore, fluoresceins (e.g., aminofluorescein) and drugs (e.g., doxorubicin) with free amino groups can be conjugated onto the network of the dextran-based microgel via Schiff base linkages. Since the Schiff base linkages are degradable via hydrolysis and their stability decreases with the environmental pH decreases, the resulted Schiff bases contained microgel showed a pH dependent degradation profile. These results indicated that the pH-sensitive microgel based on dextran could be used as promising drug delivery systems for biomedical applications.