Progress in Preparation of Sea Urchin-like Micro-/Nanoparticles.

Urchin-like microparticles/nanoparticles assembled from radial nanorods have a good appearance and high specific surface area, providing more exposed active sites and shortening the diffusion path of photoexcited carriers from the interior to the surface. The interfacial interaction and physical and chemical properties of the materials can be improved by the interfacial porous network induced by interlacing nano-branches. In addition, multiple reflections of the layered microstructure can absorb more incident light and improve the photocatalytic performance. Therefore, the synthesis and functionalization of three-dimensional urchin-like nanostructures with controllable size, shape, and hierarchy have attracted extensive attention. This review aims to provide an overview to summarize the structures, mechanism, and application of urchin-like microparticles/nanoparticles derived from diverse synthesis methods and decoration types. Firstly, the synthesis methods of solid urchin-like micro-/nanoparticles are listed, with emphasis on the hydrothermal/solvothermal method and the reaction mechanism of several typical examples. Subsequently, the preparation method of composite urchin-like micro-/nanoparticles is described from the perspective of coating and doping. Then, the research progress of urchin-like hollow microspheres is reviewed from the perspective of the step-by-step method and synchronous method, and the formation mechanism of forming urchin-like hollow microspheres is discussed. Finally, the application progress of sea urchin-like particles in the fields of photocatalysis, electrochemistry, electromagnetic wave absorption, electrorheological, and gas sensors is summarized.

Ultrafast Synthesis of Urchin-Like Rutile TiO2 by Single-Step Microwave-Assisted Method.

The preparations of crystal titanium dioxide (TiO2) are often time-consuming multistep processes involving high temperature. Rapid and efficient methods to obtain TiO2 with anatase or rutile phase are desirable. In this paper, we describe an ultrafast single-step method to obtain urchin-like rutile TiO2 particles via microwave irradiation. In the procedure, TiCl4 aqueous solution was used as a reactant and toluene was used as a solvent. It takes only a few minutes without any further heat treatment. The samples were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), and thermal gravimetric analysis (TGA). The effect of temperature, irradiation time and the ratio of precursor to solvent on the morphology and crystal structure were studied. The results show urchin-like rutile TiO2 with high stability is formed after only 5 min microwave irradiation at 135 °C.

Wet-Chemical Preparation of TiO2-Based Composites with Different Morphologies and Photocatalytic Properties.

TiO2-based composites have been paid significant attention in the photocatalysis field. The size, crystallinity and nanomorphology of TiO2 materials have an important effect on the photocatalytic efficiency. The synthesis and photocatalytic activity of TiO2-based materials have been widely investigated in past decades. Based on our group's research works on TiO2 materials, this review introduces several methods for the fabrication of TiO2, rare-earth-doped TiO2 and noble-metal-decorated TiO2 particles with different morphologies. We focused on the preparation and the formation mechanism of TiO2-based materials with unique structures including spheres, hollow spheres, porous spheres, hollow porous spheres and urchin-like spheres. The photocatalytical activity of urchin-like TiO2, noble metal nanoparticle-decorated 3D (three-dimensional) urchin-like TiO2 and bimetallic core/shell nanoparticle-decorated urchin-like hierarchical TiO2 are briefly discussed.

Influence of Side Chain Sizes on Dielectric and Electrorheological Responses of Poly(ionic liquid)s.

Poly(ionic liquid)s (PILs) show potential as new anhydrous polyelectrolyte-based smart electrorheological (ER) materials. Understanding the structure-property relationship on a molecular level is very important for guiding the design of PIL-based ER materials. In this paper, a family of (p-vinylbenzyl)trialkylammonium hexafluorophosphate-based PIL particles containing different length of substituent alkyl chains attached to immobile ammonium charged site is synthesized for especially understanding the size effect of side chains on ER property. To exclude the particle shape effect, the PIL particles are controlled to be monodisperse sphere-like morphology with a similar size. The ER property of PIL particles when dispersed in insulating oil is investigated and compared by temperature-modulated rheological test under external electric fields. The dielectric spectroscopy is finally performed to study the mechanism behind the size effect of side chains on the ER property of PIL particles. We demonstrate that the size of side chains on the charged site has a significant impact on the ER effect of PIL particles and the PIL particles with shorter side chains have stronger ER property but degraded temperature dependence, and this is related to the fact that the variation of side chain size alters the transport dynamic of mobile counterions and ion motion-induced interfacial polarization.

Bimetallic core/shell nanoparticle-decorated 3D urchin-like hierarchical TiO2 nanostructures with magneto-responsive and decolorization characteristics.

The semiconductors decorated with noble metals or magnetic metals have attracted increasing attention due to multifunctional properties. In this article, we prepare novel bimetallic core/shell nanoparticle (Co@Au and Co@Ag)-decorated 3D urchin-like hierarchical TiO2 nanostructures through combining electroless plating and in situ replacement processes. The morphology and structure are characterized by scanning electron microscopy, transmission electron microscopy, energy-dispersive spectroscopy, and a surface area analyzer. It demonstrates that Co@Au and Co@Ag nanoparticles are uniformly decorated on urchin-like TiO2 nanostructures. The composite nanostructures show not only surface plasmon absorption band from Au or Ag but also a magneto-responsive characteristic from Co. This allows composite nanostructures to exhibit advantages including enhanced decolorization efficiency compared to pure TiO2 nanostructures and facile separation from a solution by magnetic field.

Au or Ag nanoparticle-decorated 3D urchin-like TiO2 nanostructures: synthesis, characterization, and enhanced photocatalytic activity.

The semiconductors decorated with noble metals have attracted increasing attention due to their interesting physical and chemical properties. Here, 3D urchin-like hierarchical TiO2 nanostructures decorated with Au or Ag nanoparticles were prepared by wet-chemical process. The morphology and structure were characterized by different techniques. It shows that Au or Ag nanoparticles with narrow distribution are uniformly loaded on urchin-like TiO2 nanostructures, and the resulted composite nanostructures show distinct surface plasmon absorption band and quenched photoluminence compared to pure TiO2 nanostructures. Photocatalytic tests show both Au-decorated TiO2 and Ag-decorated TiO2 exhibit enhanced photocatalytic activity for photodegradation of methyl blue in water.

Preparation of montmorillonite/titania nanocomposite and enhanced electrorheological activity.

We prepared a new type of electrorheological particle composed of TiO2 nanocrystallites-coated montmorillonite (MMT/TiO2) nanocomposite by the sol-gel technique. The characterizations including TGA, XRD, TEM, SEM, EDS, and FTIR showed that TiO2 was deposited on the surface of the MMT flakes with anatase nanocrystallite. An obviously enhanced ER effect was found in the MMT/TiO2 nanocomposites based ER fluids compared with pure MMT and TiO2. Furthermore, the temperature and sedimentation stabilities of the MMT/TiO2 ER fluids had also been improved greatly. Interestingly, the content of TiO2 was demonstrated to have an important influence on the ER effect. When the content of TiO2 was about 20 wt%, the ER effect of MMT/TiO2 ER fluid reached its maximum, which was about 5 times that of pure MMT ER fluid and 27 times that of pure TiO2 ER fluid. Based on dielectric analysis, the significant ER enhancement by formation nanocrystallites-coated montmorillonite was attributed to the enhanced interfacial polarization in this nanocomposite particle due to the effective limitation of the long-range drift of active ions in montmorillonite particles.