In this work, the exceptionally improved sensing capability of highly porous 3-D hybrid ceramic networks with respect to reducing gases is demonstrated for the first time. The 3-D hybrid ceramic networks are based on metal oxides Me= Fe, Cu, Al) doped and alloyed zinc oxide tetrapods (ZnO-T) forming numerous heterojunctions. A change in morphology of the samples and formation of different complex microstructures is achieved by mixing the metallic (Fe, Cu, Al) microparticles with ZnO tetrapods grown by flame transport synthesis (FTS) approach with different weight ratios (ZnO:Me, e.g., 20:1) and followed by subsequent thermal annealing them in air. The gas sensing studies reveal the possibility to control and change/tune the selectivity of the materials, depending on the elemental content ratio and the type of the added metal oxide in 3-D ZnO-T hybrid networks.While pristine ZnO-T networks showed a good response to H2 gas, a change/tune in selectivity to ethanol vapour with a decrease in optimal operating temperature was observed in the networks hybridized with Fe-oxide and Cu-oxide. In case of hybridization with ZnAl2O4 an improvement of H2 gas response (to ≈ 7.5) was reached at lower doping concentrations (20:1), whereas the increasing in concentration of ZnAl2O4 (10:1), the selectivity changes to methane CH4 gas (response ≈ 28). Selectivity tuning to different gases is attributed to the catalytic properties of the metal oxides after hybridization, while the sensitivity improvement is mainly associated with additional modulation of resistance by the built-in potential barriers between n-n and n-p heterojunctions, during adsorption and desorption of gaseous species. Density functional theory based calculations provided the mechanistic insights into the interactions between different hybrid networks and gas molecules supporting the experimentally observed results. The studied materials and sensor structures would provide particular advantages in the field of fundamental research, industrial and ecological applications.
Hybrid metal oxide nano-and microstructures exhibit novel properties, which make them promising candidates for a wide range of applications, including gas sensing. In this work, the characteristics of the hybrid ZnOBi 2 O 3 and ZnO-Zn 2 SnO 4 tetrapod (T) networks are investigated in detail. The gas sensing studies reveal improved performance of the hybrid networks compared to pure ZnO-T networks. For the ZnO-T-Bi 2 O 3 networks, an enhancement in H 2 gas response is obtained, although the observed p-type sensing behavior is attributed to the formed junctions between the arms of ZnO-T covered with Bi 2 O 3 and the modulation of the regions where holes accumulate under exposure to H 2 gas. In ZnO-T-Zn 2 SnO 4 networks, a change in selectivity to CO gas with high response is noted. The devices based on individual ZnO-T-Bi 2 O 3 and ZnO-T-Zn 2 SnO 4 structures showed an enhanced H 2 gas response, which is explained on the basis of interactions (electronic sensitization) between the ZnO-T arm and Bi 2 O 3 shell layer and single Schottky contact structure, respectively. Density functional theory-based calculations provide mechanistic insights into the interaction of H 2 and CO gas molecules with Bi-and Sn-doped ZnO(0001) surfaces, revealing changes in the Fermi energies, as well as charge transfer between the molecules and surface species, which facilitate gas sensing.
The present work reports the synthesis of zinc oxide (ZnO) nanostructures produced either under microwave irradiation using low cost domestic microwave equipment or by conventional heating, both under hydrothermal conditions. X-ray diffraction, scanning electron microscopy, Fourier transform infrared spectroscopy, room/low temperature photoluminescence, and Raman spectroscopy have been used to investigate the structure, morphology, and optical properties of the produced ZnO nanorods. Identical structures with aspect ratio up to 13 have been achieved for both synthesis routes displaying similar final properties. The hexagonal wurtzite structure has been identified, and a red-orange emission has been detected in the presence of UV irradiation for all the conditions studied. Thermal stability of the as-prepared nanostructures has been evaluated through thermogravimetric measurements revealing an increase of superficial defects. The as-prepared ZnO nanorods were tested as UV sensors on paper substrate, which led to fast response (30 s) and rapid recovery (100 s) times, as well as sensitivity up to 10 indicating that these materials may have a high potential in low cost, disposable UV photodetector applications.
The present work reports the synthesis of zinc oxide (ZnO) nanoparticles with hexagonal wurtzite structure considering a solvothermal method assisted by microwave radiation and using different solvents: water (H 2 O), 2-ethoxyethanol (ET) and ethylene glycol (EG). The structural characterization of the produced ZnO nanoparticles has been accessed by scanning electron microscopy, X-ray diffraction, room-temperature photoluminescence and Raman spectroscopies. Different morphologies have been obtained with the solvents tested. Both H 2 O and ET resulted in rods with high aspect ratio, while EG leads to flower-like structure. The UV absorption spectra showed peaks with an orange shift for synthesis with H 2 O and ET and blue shift for synthesis with EG. The different synthesized nanostructures were tested for photocatalyst applications, revealing that the ZnO nanoparticles produced with ET degrade faster the molecule used as model dye pollutant, i.e. methylene blue. Graphical AbstractIntroduction
ZnO microrods were grown by laser assisted flow deposition technique in order to study their luminescence behaviour in the near band edge spectral region. Transmission electron microscopy analysis put in evidence the high crystallinity degree and microrod’s compositional homogeneity. Photoluminescence revealed a dominant 3.31 eV emission. The correlation between this emission and the presence of surface states was investigated by performing plasma treatments with hydrogen and nitrogen. The significant modifications in photoluminescence spectra after the plasma treatments suggest a connexion between the 3.31 eV luminescence and the surface related electronic levels.
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