Polydopamine-modification of a magnetic composite constructed from citric acid-cross-linked cyclodextrin and graphene oxide for dye removal from waters.

The effect of polydopamine (PDA) modification on aminated Fe3O4 nanoparticles (Fe3O4-NH2)/graphite oxide (GO)/ß-cyclodextrin polymer cross-linked by citric acid (CDP-CA) composites were studied for the removal of a cationic dye (methylene blue, MB) and an anionic dye (Congo red, CR) from waters. The micro-structural and magnetic characterizations confirmed the successful preparation of Fe3O4-NH2/GO/CDP-CA and PDA/Fe3O4-NH2/GO/CDP-CA composites. The maximum MB and CR adsorption capacities of Fe3O4-NH2/GO/CDP-CA were 75 mg/g and 104 mg/g, respectively, while the corresponding amounts for PDA/Fe3O4-NH2/GO/CDP-CA composite were 195 mg/g and 64 mg/g, respectively. The dye sorption behaviors of these two composites were explained by their corresponding surface-charged properties according to the measured zeta potential results. Moreover, the high saturation magnetizations and the stable dye removal rate in the adsorption-desorption cycles indicated the good recyclability and reusability of the fabricated composites.

Engineering Surface and Optical Properties of TiO2-Coated Electrospun PVDF Nanofibers Via Controllable Self-Assembly.

Understanding the effect of a porous TiO2 nanolayer on the optical scattering and absorption through electrospun fibers is of great importance for the design and development of advanced optical extinction materials. Based on electrospinning and controllable self-assembly techniques, pure electrospun poly(vinylidene fluoride) (PVDF) fibers and TiO2-coated ones with different self-assembly cycles were prepared. The effect of TiO2 self-assembly cycles on surface parameters, e.g., thickness, assembled content, and porosity of the TiO2 nanolayer were determined by scanning electron microscopy, thermogravimetric analysis, and Fourier transform infrared spectroscopy. With an increase in the self-assembly cycles, the TiO2-coated electrospun PVDF fibers presented rougher surfaces and greater average diameters. According to the characterized surface parameters, the effects of the controllable self-assembly on the optical refractive index, absorption index, and infrared extinction were investigated to increase the optical properties of electrospun PVDF fibers. The results indicated that an increase of almost 120⁻130 cm-1 in infrared extinction could be achieved through the controllable self-assembly with only 5.7 wt. % assembled TiO2 content. This is highly efficient when compared with other coating modes. We believe that this study could give some positive guidance in the design of TiO2-coated electrospun fibers for improving their surface and optical properties.

Preparation of Nanofibrous Silver/Poly(vinylidene fluoride) Composite Membrane with Enhanced Infrared Extinction and Controllable Wetting Property.

Nanofibrous silver (Ag)/poly(vinylidene fluoride) (PVDF) composite membranes were obtained from a two-step preparation method. In the first step, the electrospun silver nitrate (AgNO3)/PVDF membranes were prepared and the influence of the AgNO3 content on the electrospinning process was studied. According to scanning electron microscopy (SEM) results, when the electrospinning solution contained AgNO3 in the range between 3 to 7 wt.%, the nanofiber morphologies can be obtained. In the second step, the electrospun AgNO3/PVDF membranes were reduced by sodium borohydride to form the nanofibrous Ag/PVDF composite membranes. The resultant composite membranes were characterized by SEM, X-ray diffraction (XRD), energy-dispersive spectroscopy (EDS), differential scanning calorimetry, X-ray photoelectron spectroscopy (XPS), and Fourier-transform infrared. The XRD, XPS, and EDS characterizations proved the existence of Ag in the nanofibrous Ag/PVDF composite membranes. The crystallinity degree of PVDF for composite membranes declined with the increase in Ag content. More importantly, the nanofibrous Ag/PVDF composite membranes had obviously higher Rosseland extinction coefficients and lower thermal radiative conductivities in comparison with electrospun PVDF membrane, which demonstrates that such composite membranes with high porosity, low density, and good water vapor permeability are promising thermal insulating materials to block the heat transfer resulting from thermal radiation. In addition, three different methods for surface modification have been used to successfully improve the hydrophobicity of nanofibrous Ag/PVDF composite membranes.

Surface Modification of Electrospun Poly(vinylidene fluoride) Fibrous Membrane Based on Layer-by-Layer Assembly of TiO 2 Nanoparticles.

A facile surface modification method of improving hydrophilicity of poly(vinylidene fluoride) (PVDF) membranes was presented by layer-by-layer assembly. Various layers of anatase TiO2 nanoparticles were successfully deposited on electrospun PVDF fibrous membranes. FTIR, SEM, TEM and droplet scanning analysis were used to investigate microstructure and contact angle (CA) of modified membranes. TiO2 modified PVDF fibers showed rougher surface and greater diameter compared to uncoated ones. The CA of modified membranes was significantly decreased. For instance, the CA of the 4 layers of TiO2 modified membranes through two pretreatment methods (viz., ethanol-water displacement or KMnO4 modification) could be decreased to 0° while the unmodified PVDF had CA of 114.4°. Moreover, the modification through ethanol-water pre-treatment formed TiO2 coating owing to hydrogen bonds without damaging strength of PVDF. Therefore, this presents a facile and effective hydrophilic modification method for PVDF in water treatment, filtration and other fields.

From vesicles to micelles: microphase separation of amphiphilic dendrimer copolymers in a selective solvent.

The microphase separation of amphiphilic dendrimer copolymers in a selective solvent with different excluded volume effects (αS) is investigated using three-dimensional real space self-consistent field theory. The morphological transition of disorder-to-order and order-to-order is observed by systematically regulating the excluded volume effect parameter, interaction parameter of block species, and the spacer length of the second generation of the dendrimer. The ordered segregates of the dendrimer solution are observed with a stronger excluded volume effect due to the strong depletion effect of solvent on the dendrimer. The relative magnitude between hydrophobic block B and hydrophilic block C is very important for microphase separation: when they are equal (NB = NC), a structural shift from vesicles to micelles has been found upon increasing the interaction parameter, and the region of disordered morphology is controlled by the interfacial free energy (Uint); when NB > NC, the vesicular morphologies overwhelmingly appear in the ordered region and then NC increases to close to NB, and the ordered aggregates take a shift from vesicles to micelles. Furthermore, the amphiphilic block C of the dendrimer is intended to enlarge to NC > NB, the micellar morphology is dominant in the ordered regime with a stronger excluded volume effect, which contributes to the decrease in the hydrophobic block repulsion that is affected by the decrease in the entropic free energy (-TS). The knowledge obtained from the microphase separation of dendrimer solution induced by the excluded volume effect of selective solvent is full of referential significance in understanding the morphological transition from vesicles to micelles for the amphiphile in the field of soft matter.

Fabrication of hybrids based on graphene and metal nanoparticles by in situ and self-assembled methods.

In this work, we developed two novel strategies to attach metal nanoparticles (Au and Ag) to the surface of graphene nanosheets, in which graphene oxide was first modified by the linking molecule (3-mercaptopropyl)triethoxysilane and then subjected to different treatments including in situ and self-assembled techniques. The synthesis processes and the resulting hybrids were investigated by ultraviolet-visible measurements, scanning electron microscopy, transmission electron microscopy, and X-ray photoelectron spectroscopy. It was found that both approaches could effectively immobilize metal nanoparticles onto a graphene surface, and that better distribution and size control of metal nanoparticles were obtained by the self-assembled method. Moreover, we prepared poly(vinylidene fluoride)/graphene-Ag nanocomposites by a solution blending method. The AC conductivity of the resulting nanocomposites could be increased significantly when the loading amount of graphene-Ag was only 2 wt%. We expect that such graphene-metal nanoparticle hybrids may be potentially useful in composite reinforcement, sensors, and electronic devices.

Organo-modified ZnAl layered double hydroxide as new catalyst support for the ethylene polymerization.

Organo-modified ZnAl layered double hydroxide was used for the first time to support a nickel a-diimine catalyst for the ethylene polymerization, and its effects on the catalytic activity, the morphology, thermal stability, and dynamic viscoelastic properties of the resultant polyethylene material were investigated. Different from the homogeneous nickel a-diimine catalyst, the supported catalyst system was found to have a long-lasting polymerization activity. Moreover, the resultant polyethylene material showed good particle morphology, improved thermal stability, as well as enhanced storage modulus and complex viscosity.