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.

Three-dimensional (3D) assemblies based on carbon nanomaterials still lag behind their individual one-dimensional building blocks in terms of mechanical and electrical properties. Here we demonstrate a simple strategy for the fabrication of an open porous 3D self-organized double-hierarchical carbon nanotube tube structure with properties advantageous to those existing so far. Even though no additional crosslinking exists between the individual nanotubes, a high reinforcement effect in compression and tensile characteristics is achieved by the formation of self-entangled carbon nanotube (CNT) networks in all three dimensions, employing the CNTs in their high tensile properties. Additionally, the tubular structure causes a self-enhancing effect in conductivity when employed in a 3D stretchable conductor, together with a high conductivity at low CNT concentrations. This strategy allows for an easy combination of different kinds of low-dimensional nanomaterials in a tube-shaped 3D structure, enabling the fabrication of multifunctional inorganic-carbon-polymer hybrid 3D materials.

Buckminster fullerene (C60) based hybrid metal oxide materials are receiving considerable attention because of their excellent fundamental and applied aspects, like semiconducting, electron transfer, luminescent behaviors, etc. and this work briefly discusses the successful fabrication of C60 decorated ZnO tetrapod materials and their detailed structure-property relationships including device sensing applications. The electron microscopy investigations indicate that a quite dense surface coverage of ZnO tetrapods with C60 clusters is achieved. The spectroscopy studies confirmed the identification of the C60 vibrational modes and the C60 induced changes in the absorption and luminescence properties of the ZnO tetrapods. An increased C60 concentration on ZnO results in steeper ZnO bandgap absorption followed by well-defined free exciton and 3.31 eV line emissions. As expected, higher amounts of C60 increase the intensity of C60-related visible absorption bands. Pumping the samples with photons with an energy corresponding to these absorption band maxima leads to additional emission from ZnO showing an effective charge transfer phenomenon from C60 to the ZnO host. The density of states model obtained from DFT studies for pure and C60 coated ZnO surfaces confirms the experimental observations. The fabricated C60-ZnO hybrid tetrapod based micro- and nanodevices showed interesting ethanol gas sensing characteristics.