To get a real understanding on the complexity of origin and mechanism of visible emission for ZnO quantum dots (QDs), we systematically property of visible emission of ZnO QDs with tunable diameters in a range of 2.2−7.8 nm synthesized via a sol−gel route using self-made zinc−oleate complex as a precursor. It is indicated that the visible emission of ZnO QDs can be ascribed to singly ionized oxygen vacancies, which is associated with the paramagnetic centers with electron paramagnetic resonance (EPR) value of g = 2.0056. The visible emission property of the ZnO QDs displays highly size-dependent behavior. With ZnO QDs size decreasing, the visible emission peaks blue-shift to the positions with shorter wavelength due to quantum size effect, however, is different from that of band gap. Quantitative investigation shows that the visible emission can correspond to a transition of holes from the valence band to the preexisting deep donor energy level, which is different from the well-known conclusion that the visible emission is due to the transition of an electron from the conduction band to a deep trap. Two important points can be obtained: the defects of singly ionized oxygen vacancies determine the origin and intensity of visible emission of ZnO QDs; and the visible emission peak position of ZnO QDs is decided by their size, and a transition of holes from the valence band to the preexisting deep donor energy level is responsible for the visible emission of the ZnO QDs.
Interconnected hollow carbon nanospheres (HCNSs) were prepared by pressure‐assisted reduction and graphitization of sucrose in autoclaves without template. The obtained HCNSs with a large surface area, very thin graphitic shells, and an interconnected structure exhibit excellent performances as the electrode material for lithium ion batteries.
Three-dimensional (3D) crystalline anatase titanium dioxide (TiO(2)) hierarchical nanostructures were synthesized through a facile and controlled hydrothermal and after-annealing process. The formation mechanism for the anatase TiO(2) 3D hierarchical nanostructures was investigated in detail. The 3D hierarchical nanostructures morphologies are formed by self-organization of several tens of radially distributed thin petals with a thickness of several nanometers with a larger surface area. The surface area of TiO(2) hierarchical nanostructures determined by the Brunauer-Emmett-Teller (BET) adsorption isotherms was measured to be 64.8 m(2) g(-1). Gas sensing properties based on the hierarchical nanostructures were investigated. A systematic study on sensitivity as a function of temperatures and gas concentrations was carried out. It reveals an improved ethanol gas sensing response property with a sensitivity of about 6.4 at 350 degrees C upon exposure to 100 ppm ethanol vapor for the TiO(2) hierarchical nanostructures. A gas sensing mechanism based on the adsorption-desorption of oxygen on the surface of TiO(2) is discussed and analyzed. This novel gas sensor can be multifunctional and promising for practical applications. Furthermore, the hierarchical nanostructures with high surface area can find variety of potential applications such as solar cells, biosensors, catalysts, etc.
Bulk quantities of hexagonal boron nitride (h-BN) nanosheets have been synthesized via a simple template- and catalyst-free chemical vapor deposition process at 1100−1300 °C. Adjusting the synthesis and chemical reaction parameters, the thickness of the BN nanosheets can be tuned in a range of 25−50 nm. Fourier transform infrared spectra and electron energy loss spectra reveal the typical nature of sp2-hybridization for the BN nanosheets. It shows an onset oxidation temperature of 850 °C for BN nanosheets compared with only about 400 °C for that of carbon nanotubes under the same conditions. It reveals a strong and narrow cathodoluminescence emission in the ultraviolet range from the h-BN nanosheets, displaying strong ultraviolet lasing behavior. The fact that this luminescence response would be rather insensitive to size makes the BN nanosheets ideal candidates for lasing optical devices in the UV regime. The h-BN nanosheets are also better candidates for composite materials in high-temperature and hazardous environments.
Highly crystalline Pt nanoparticles with an average diameter of 5 nm were homogeneously modified on the surfaces of TiO(2) nanowires (Pt-TiO(2) NWs) by a simple hydrothermal and chemical reduction route. Photodegradation of methylene blue (MB) in the presence of Pt-TiO(2) NWs indicates that the photocatalytic activity of TiO(2) NWs can be greatly enhanced by Pt nanoparticle modification. The physical chemistry process and photocatalytic mechanism for Pt-TiO(2) NWs hybrids degrading MB were investigated and analyzed. The Pt attached on TiO(2) nanowires induces formation of a Schottky barrier between TiO(2) and Pt naonoparticles, leading to a fast transport of photogenerated electrons to Pt particles. Furthermore, Pt incoporation on TiO(2) surface can accelerate the transfer of electrons to dissolved oxygen molecules. Besides enhancing the electron-hole separation and charge transfer to dissolved oxygen, Pt may also serve as an effective catalyst in the oxidation of MB. However, a high Pt loading value does not mean a high photocatalytic activity. Higher content loaded Pt nanoparticles can absorb more incident photons which do not contribute to the photocatalytic efficiency. The highest photocatalytic activity for the Pt-TiO(2) nanohybrids on MB can be obtained at 1 at % Pt loading.
The hexagonal faceted ZnO quantum dots (QDs) about 3-4 nm have been prepared via a sol-gel route by using oleic acid (OA) as the capping agent. It is revealed by electron diffraction patterns and high resolution transmission electron microscopy lattice images that the profile surfaces of the highly crystalline ZnO QDs are mainly composed of {100} planes, with the Zn-terminated (001) faces and the opposite (001) faces presented as polar planes. Compared with spherical ZnO QDs, the hexagonal faceted ZnO QDs show enhanced photocatalytic activity for photocatalytic decomposition of methylene blue. A mechanism for the enhanced photocatalytic activity of the hexagonal faceted ZnO QDs for degradation of methylene blue is proposed. In addition to the large specific surface areas due to small size and high crystalline, the enhanced photocatalytic activity can mainly be ascribed to the special hexagonal morphology. The Zn-terminated (001) and O-terminated (001) polar faces are facile to adsorb oxygen molecules and OH(-) ions, resulting in a greater production rate of H(2)O(2) and OH(*) radicals, hence promoting the photocatalysis reaction. The synthesized hexagonal-shaped ZnO QDs with high photocatalytic efficiency will find widespread potential applications in environmental and biological fields.
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