Growth of freestanding nano- and microstructures with complex morphologies is a highly desired aspect for real applications of nanoscale materials in various technologies. Zinc oxide tetrapods (ZnO-T), which exhibit three-dimensional (3D) shapes, are of major importance from a technological applications point of view, and thus efficient techniques for growth of different varieties of tetrapod-based networks are demanded. Here, we demonstrate the versatile and single-step synthesis of ZnO-T with different arm morphologies by a simple flame transport synthesis (FTS) approach, forming a network. Morphological evolutions and structural intactness of these tetrapods have been investigated in detail by scanning electron microscopy, X-ray diffraction, and micro-Raman measurements. For a deeper understanding of the crystallinity, detailed high-resolution transmission electron microscopic studies on a typical ZnO tetrapod structure are presented. The involved growth mechanism for ZnO tetrapods with various arm morphologies is discussed with respect to variations in experimental conditions. These ZnO-T have been utilized for photocatalytic degradation and nanosensing applications. The photocatalytic activities of these ZnO-T with different arm morphologies forming networks have been investigated through the photocatalytic decolorization of a methylene blue (MB) solution under UV light illumination at ambient temperature. The results show that these ZnO-T exhibit strong photocatalytic activities against MB and its complete degradation can be achieved in very short time. In another application, a prototype of nanoelectronic sensing device has been built from these ZnO-T interconnected networks and accordingly utilized for UV detection and H2 gas sensing. The fabricated device structures showed excellent sensing behaviors for promising practical applications. The involved sensing mechanisms with respect to UV photons and H2 gas are discussed in detail. We consider that such multifunctional nanodevices based on ZnO tetrapod interconnected networks will be of interest for various advanced applications.

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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.

A cost-effective synthesis was used to grow ZnxCu1−xOy nanostructures. DFT calculations show that charge transfer along with changes in Fermi level facilitate H2 gas sensing, which is further enhanced by Zn doping.

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