ZnO materials with a range of different morphologies have been synthesized via a simple solvothermal method with different solvents. Zinc acetylacetonate was used as the zinc source in such solvothermal syntheses for the first time. XRD data showed that single-phase ZnO with the wurtzite crystal structure was obtained for all the solvents used. FE-SEM imaging showed that ZnO with cauliflower-like, truncated hexagonal conical, tubular and rodlike, hourglass-like, nanorods, and spherical shapes were produced when THF, decane, water, toluene, ethanol, and acetone were used as the solvent, respectively. The TEM data showed that the crystalline ZnO had different growth habits in the different solvents. The optical properties of the as-prepared ZnO materials were investigated by UV-vis absorption and room temperature photoluminescence. Photodegradation of phenol was used as a model reaction to test the photocatalytic activity of the ZnO samples. ZnO samples with different morphologies and crystal growth habits exhibited different activities to phenol degradation. The ZnO material prepared using THF as the solvent showed a nine-times enhancement of the kinetic rate constants over commercial ZnO (0.1496 min -1 vs 0.0182 min -1 ). The influence of the solvents on the morphology of ZnO samples and the effect of the morphologies on the photocatalytic activity are discussed.
Hybrid nanomaterials are molecular or colloidal-level combinations of organic and inorganic materials, or otherwise strongly dissimilar materials. They are often, though not exclusively, anisotropic in shape. A canonical example is an inorganic nanorod or nanosheet sheathed in, or decorated by, a polymeric or other organic material, where both the inorganic and organic components are important for the properties of the system. Hybrid nanomaterials and nanocomposites have generated strong interest for a broad range of applications due to their functional properties. Generating macroscopic assemblies of hybrid nanomaterials and nanomaterials in nanocomposites with controlled orientation and placement by directed assembly is important for realizing such applications. Here, a survey of critical issues and themes in directed assembly of hybrid nanomaterials and nanocomposites is provided, highlighting recent efforts in this field with particular emphasis on scalable methods.
An entirely bottom‐up approach for the preparation of liquid crystalline suspensions of core‐shell nanowires for ordered bulk heterojunction photovoltaics is demonstrated. Side‐on attachment of polythiophene derivatives to ZnO nanowires promotes a co‐axial polymer backbone‐nanowire arrangement which favors high hole mobility. This strategy offers structural control over multiple length scales and a viable means of fabricating ordered films over large areas.
Controlled alignment of nanomaterials over large length scales (>1 cm) presents a challenge in the utilization of low-cost solution processing techniques in emerging nanotechnologies. Here, we report on the lyotropic liquid crystalline behavior of transition-metal-doped zinc oxide nanowires and their facile alignment over large length scales under external fields. High aspect ratio Co- and Mn-doped ZnO nanowires were prepared by solvothermal synthesis with uniform incorporation of dopant ions into the ZnO wurtzite crystal lattice. The resulting nanowires exhibited characteristic paramagnetic behavior. Suspensions of surface-functionalized doped nanowires spontaneously formed stable homogeneous nematic liquid crystalline phases in organic solvent above a critical concentration. Large-area uniaxially aligned thin films of doped nanowires were obtained from the lyotropic phase by applying mechanical shear and, in the case of Co-doped nanowires, magnetic fields. Application of shear produced thin films in which the nanowire long axes were aligned parallel to the flow direction. Conversely, the nanowires were found to orient perpendicular to the direction of the applied magnetic fields. This indicates that the doped ZnO possesses magnetocrystalline anisotropy sufficient in magnitude to overcome the parallel alignment which would be predicted based solely on the anisotropic demagnetizing field associated with the high aspect ratio of the nanowires. We use a combination of magnetic property measurements and basic magnetostatics to provide a lower-bound estimate for the magnetocrystalline anisotropy.
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