In this research work, the sensitivity of TiO2 nanoparticles towards C2H5OH, H2 and CH4 gases was investigated. The morphology and phase content of the particles was preserved during sensing tests by prior heat treatment of the samples at temperatures as high as 750 °C and 1000 °C. Field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM) and X-ray diffraction (XRD) analysis were employed to characterize the size, morphology and phase content of the particles. For sensor fabrication, a film of TiO2 was printed on a Au interdigitated alumina substrate. The sensing temperature was varied from 450 °C to 650 °C with varying concentrations of target gases. Results show that the sensor has ultrahigh response towards ethanol (C2H5OH) compared to hydrogen (H2) and methane (CH4). The optimum sensing temperature was found to be 600 °C. The response and recovery times of the sensor are 3 min and 15 min, respectively, for 20 ppm C2H5OH at the optimum operating temperature of 600 °C. It is proposed that the catalytic action of TiO2 with C2H5OH is the reason for the ultrahigh response of the sensor.
Recently one dimensional (1-D) nanostructured metal-oxides have attracted much attention because of their potential applications in gas sensors. 1-D nanostructured metal-oxides provide high surface to volume ratio, while maintaining good chemical and thermal stabilities with minimal power consumption and low weight. In recent years, various processing routes have been developed for the synthesis of 1-D nanostructured metal-oxides such as hydrothermal, ultrasonic irradiation, electrospinning, anodization, sol-gel, molten-salt, carbothermal reduction, solid-state chemical reaction, thermal evaporation, vapor-phase transport, aerosol, RF sputtering, molecular beam epitaxy, chemical vapor deposition, gas-phase assisted nanocarving, UV lithography and dry plasma etching. A variety of sensor fabrication processing routes have also been developed. Depending on the materials, morphology and fabrication process the performance of the sensor towards a specific gas shows a varying degree of success. This article reviews and evaluates the performance of 1-D nanostructured metal-oxide gas sensors based on ZnO, SnO(2), TiO(2), In(2)O(3), WO(x), AgVO(3), CdO, MoO(3), CuO, TeO(2) and Fe(2)O(3). Advantages and disadvantages of each sensor are summarized, along with the associated sensing mechanism. Finally, the article concludes with some future directions of research.
In this research work, nanowires were grown on brass (Cu - 37.2 wt% Zn) substrate by thermal oxidation process. The substrate was oxidized at temperature ranging from 350-600 °C in the presence of varying concentrations of O2 in N2 (1-100%) flown at a rate of 200 sccm. The oxidized brass surface was characterized by field emission scanning electron microscope (FESEM) equipped with energy dispersive X-ray (EDX) spectroscope and transmission electron microscope (TEM). Four different types of morphological variations such as thin, thick with branches, circular-flake and flat-cone shape were observed during oxidation at different conditions. However, the prevalence of thin, thick morphology with branches was more prominent and found in all growth conditions. The length and diameter of the nanowires were varied from 1-30 µm and 50-500 nm, respectively whereas the length of the branches varied from 1-3 µm. The composition of the nanowires was ZnO possessing of hexagonal wurtzite structure. The selected area diffraction confirms that the nanowires grew along <1 1 0> directions. Based on the results, a stress induced based mechanism is proposed for the growth of ZnO nanowires on Cu - 37.2 wt% Zn substrate.
Different Ti substrates, such as particles (as-received and ball milled), plate and TEM grid were oxidized for the growth of one dimensional (1D) TiO2nanostructures. The Ti substrates were oxidized for 4 h at temperatures of 700 °C-750 °C in humid and dry Ar containing 5 ppm of O2. The effects of residual stress on the growth of 1D TiO2nanostructures were investigated. The residual stress inside the Ti particles was measured by XRD-sin2ψtechnique. The oxidized Ti substrates were characterized using field emission scanning electron microscope equipped with energy dispersive x-ray spectroscope, transmission electron microscope, x-ray diffractometer and x-ray photoelectron spectroscope. Results revealed that humid environment enhances the growth of 1D TiO2nanostructures. Four different types of 1D morphologies obtained during humid oxidation, e.g. stacked, ribbon, plateau and lamp-post shaped nanostructures. The presence of residual stress significantly enhances the density and coverage of 1D nanostructures. The as-grown TiO2nanostructures possess tetragonal rutile structure having length up to 10μm along the 〈1 0 1〉 directions. During initial stage of oxidation, a TiO2layer is formed on Ti substrate. Lower valence oxides (Ti3O5, Ti2O3and TiO) then form underneath the TiO2layer and induce stress at the interface of oxide layers. The induced stress plays significant role on the growth of 1D TiO2nanostructures. The induced stress is relaxed by creating new surfaces in the form of 1D TiO2nanostructures. A diffusion based model is proposed to explain the mechanism of 1D TiO2growth during humid oxidation of Ti. The 1D TiO2nanostructures and TiO2layer is formed by the interstitial diffusion of Ti4+ions to the surface and reacts with the surface adsorbed hydroxide ions (OH-). Lower valence oxides are formed at the metal-oxide interface by the reaction between diffused oxygen ions and Ti ions.
An ethanol gas sensor with enhanced sensor response was fabricated using Ni-doped SnO2 nanorods, synthesized via a simple hydrothermal method. It was found that the response (R = R 0/R g) of a 5.0 mol% Ni-doped SnO2 (5.0Ni:SnO2) nanorod sensor was 1.4 × 104 for 1000 ppm C2H5OH gas, which is about 13 times higher than that of pure SnO2 nanorods, (1.1 × 103) at the operating temperature of 450 °C. Moreover, for 50 ppm C2H5OH gas, the 5.0Ni:SnO2 nanorod sensor still recorded a significant response reading, namely 2.0 × 103 with a response time of 30 s and recovery time of 10 min. To investigate the effect of Ni dopant (0.5-5.0 mol%) on SnO2 nanorods, structural characterizations were demonstrated using field emission scanning electron microscopy, high-resolution transmission electron microscopy, Fourier transform infrared spectroscopy, x-ray diffraction (XRD) analysis, x-ray photoelectron spectroscopy and an ultraviolet-visible spectrometer. XRD results confirmed that all the samples consisted of tetragonal-shaped rutile SnO2 nanorods. It was found that the average diameter and length of the nanorods formed in 5.0Ni:SnO2 were four times smaller (∼6 and ∼35 nm, respectively) than those of the nanorods formed in pure SnO2 (∼25 and 150 nm). Interestingly, both samples had the same aspect ratio, ∼6. It is proposed that the high response of the 5.0Ni:SnO2 nanorod sensor can be attributed to the particle size, which causes an increase in the thickness of the charge depletion layer, and the presence of oxygen vacancies within the matrix of SnO2 nanorods.
Tin (IV) oxide (SnO2) nanostructures are regarded as one of the most popular materials for conventional gas sensors, due to their high surface area and fast response in regard to most reducing and oxidizing gases. However, their high operating temperature (>200 °C) leads to high power consumption and limits their applications. Here, a new nanocomposite fiber materials, consisting of undoped and doped (nickel and palladium) SnO2 nanorods, polyaniline (PANI), and polyhydroxy-3-butyrate (P3HB) are synthesized via the hydrothermal method,followed by an in situ polymerization and electrospinning technique. The as-synthesized nanocomposites are tested using ethanol gas at different operating temperatures: 25 °C (room temperature), 60 °C, and 80 °C. The results reveal that all samples began to show a response at 80 °C. Pd:SnO2/PANI/P3HB nanocomposite fiber sensors demonstrate a relatively higher response than that of SnO2/PANI/P3HB and Ni:SnO2/PANI/P3HB nanocomposite sensors. At 80 °C , the Pd:SnO2/PANI/P3HB nanocomposite sensor records a response (R0/Rg ) of 1610, with a response time (Tres) of 90 s and a recovery time (Trec ) of 9 min in relation to 1000 ppm ethanol gas in N2. The sensor also displays a good level of response (R0/Rg = 200) at a low concentration level (50 ppm) of ethanol gas. Structural and chemical characterizations indicate that the ethanol gas sensing performance of Pd:SnO2/PANI/P3HB nanocomposite fibers can mainly be attributed to the p-n heterojunction, fiber geometry, and one-dimensional structure of SnO2 and to the presence of the Pd catalyst. This bio-nanocomposite fiber has the potential to be a breakthrough material in biodegradable low temperature ethanol sensing applications.