Innovative Low-Cost Carbon/ZnO Hybrid Materials with Enhanced Photocatalytic Activity towards Organic Pollutant Dyes' Removal.

A new type of material based on carbon/ZnO nanostructures that possesses both adsorption and photocatalytic properties was obtained in three stages: cellulose acetate butyrate (CAB) microfiber mats prepared by the electrospinning method, ZnO nanostructures growth by dipping and hydrothermal methods, and finally thermal calcination at 600 °C in N2 for 30 min. X-ray diffraction (XRD) confirmed the structural characteristics. It was found that ZnO possesses a hexagonal wurtzite crystalline structure. The ZnO nanocrystals with star-like and nanorod shapes were evidenced by scanning electron microscopy (SEM) measurements. A significant decrease in Eg value was found for carbon/ZnO hybrid materials (2.51 eV) as compared to ZnO nanostructures (3.21 eV). The photocatalytic activity was evaluated by studying the degradation of three dyes, Methylene Blue (MB), Rhodamine B (RhB) and Congo Red (CR) under visible-light irradiation. Therefore, the maximum color removal efficiency (both adsorption and photocatalytic processes) was: 97.97% of MB (C0 = 10 mg/L), 98.34% of RhB (C0 = 5 mg/L), and 91.93% of CR (C0 = 10 mg/L). Moreover, the value of the rate constant (k) was found to be 0.29 × 10-2 min-1. The novelty of this study relies on obtaining new photocatalysts based on carbon/ZnO using cheap and accessible raw materials, and low-cost preparation techniques.

New Electrospun ZnO:MoO3 Nanostructures: Preparation, Characterization and Photocatalytic Performance.

New molybdenum trioxide-incorporated ZnO materials were prepared through the electrospinning method and then calcination at 500 °C, for 2 h. The obtained electrospun ZnO:MoO3 hybrid materials were characterized by X-ray diffraction, scanning and transmission electron microscopies, ultraviolet (UV)-diffuse reflectance, UV-visible (UV-vis) absorption, and photoluminescence techniques. It was observed that the presence of MoO3 as loading material in pure ZnO matrix induces a small blue shift in the absorption band maxima (from 382 to 371 nm) and the emission peaks are shifted to shorter wavelengths, as compared to pure ZnO. Also, a slight decrease in the optical band gap energy of ZnO:MoO3 was registered after MoO3 incorporation. The photocatalytic performance of pure ZnO and ZnO:MoO3 was assessed in the degradation of rhodamine B (RhB) dye with an initial concentration of 5 mg/L, under visible light irradiation. A doubling of the degradation efficiency of the ZnO:MoO3 sample (3.26% of the atomic molar ratio of Mo/Zn) as compared to pure ZnO was obtained. The values of the reaction rate constants were found to be 0.0480 h-1 for ZnO, and 0.1072 h-1 for ZnO:MoO3, respectively.

Novel rare earth (RE-La, Er, Sm) metal doped ZnO photocatalysts for degradation of Congo-Red dye: Synthesis, characterization and kinetic studies.

Synthesis and characterization of novel ZnO:RE nanostructured materials doped with 1% rare-earth elements (RE = La, Er, Sm) and their testing for photocatalytic applications were reported. The materials were obtained via electrospining, followed by calcination at 700 °C. The samples were characterized in terms of surface morphology (SEM, TEM), crystalline structure (XRD) and band gap energies. TEM results showed the formation of a unidimensional structure (ZnO) with an average fiber diameter of 600 nm and a morphology consisting of interconnected nanoparticles having dimensions in the range 25-134 nm (ZnO doped with RE). Optical properties were explored by using UV-VIS reflectance spectra and the band gap values were determined with the Kubelka-Munk function (KM) by plotting [F(R∞)hν]2vs. hʋ. The photocatalytic activity was assessed by studying the degradation of a water-soluble anionic dye (Congo-Red) under UV-light irradiation. The data related to photodegradation kinetics were reasonably fitted to the pseudo-first-order kinetic model. Results revealed that the values of the rate constants ranged from 10-3 to 10-2 min-1, depending on the material type and initial dye concentration. In addition, Langmuir-Hinshelwood (LH) model was utilized to explain the kinetics of photodegradation reactions of CR in the presence of (ZnO:Sm) sample. The LH approach suggested that both adsorption and photocatalysis phenomena prevailed in the process of dye removal. Optimal conditions of experiments were determined empirically by employing the gradient method. Thus, a maximal value of color removal efficiency (95.8%) was observed experimentally for the initial dye concentration of 10.7 mg/L and 0.236 g/L catalyst dosage (ZnO:Sm). Furthermore, a successful recovery of the spent catalyst was accomplished by thermal activation.

Morphological and rheological insights on polyimide chain entanglements for electrospinning produced fibers.

Solution rheology and electrospinning performance of an aromatic polyimide based on 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA) and 3,3'-dimethyl-4,4'-diaminodiphenylmethane (MMDA) was studied. Analyzing the dependence of specific viscosity on polymer concentration enabled the evaluation of the transition from semidilute unentangled to semidilute entangled regime at 18.3%. Modification of chain interactions in solution is also reflected in a sudden increase of flow energetic barrier and consistency index values from 3.56 to 10.28 kJ/mol and 0.19 to 1.09 Pa·s(n), respectively. In the concentration domain of 15-20% the relaxation time is enhanced from 0.48 to 1.07 s, as a consequence of less chain mobility, which can be associated with the elastic character of the polyimide solution, useful for obtaining fibers. Scanning electron microscopy (SEM) and polarized light microscopy (PLM) images indicate that at 25% beaded fibers are obtained, while at 30% bead-free fibers are formed having the diameter comprised between 0.56 and 0.85 µm.