Electrospun Cu-doped ZnO nanofibers for H2S sensing

Pure and Cu-doped ZnO nanofibers were synthesized via electrospinning technology. The morphology and structure of the as-synthesized nanofibers were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and Raman spectroscopy. The effects of Cu doping on H₂S sensing properties at low concentration (1-10 ppm) were investigated at 230 °C. The results show that the H₂S sensing properties of ZnO nanofibers are effectively improved by Cu doping: 6 at% Cu-doped ZnO nanofibers show a maximum sensitivity to H₂S gas, and the response to 10 ppm H₂S is one order of magnitude higher than the one of pure ZnO nanofibers.     

Enhanced ammonia sensing performances of Pd-sensitized flowerlike ZnO nanostructure

We report the synthesis of flowerlike ZnO nanostructure using a facile hydrothermal process, and the investigation on the ammonia (NH₃)-sensing properties of the pure and palladium (Pd)-sensitized flowerlike ZnO nanostructure. The phase purity, morphology, and structure of the pure and Pd-sensitized ZnO nanostructure are investigated. The characterized results reveal that the flowerlike ZnO has a wurtzite structure and is composed of numerous aggregated single-crystalline ZnO nanorods with a diameter of about 60 nm. Having fabricated gas sensors based on the pure and Pd-sensitized flowerlike ZnO, we find that the Pd-sensitized sensor exhibits a response of 45.7-50 ppm NH₃ at 210 °C, which is about 8 times higher than that of pure ZnO at the optimal operating temperature of 350 °C. The enhanced NH₃-sensing performance demonstrates that the significant decrease in optimal operating temperature and the distinct increase in response are attributed to the sensitization effect of Pd.     

Improved selective acetone sensing properties of Co-doped ZnO nanofibers by electrospinning

Pure and Co-doped (0.3 wt%, 0.5 wt%, and 1 wt%) ZnO nanofibers are synthesized by an electrospinning method and followed by calcination. The as-synthesized nanofibers are characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and energy dispersive X-ray (EDX) spectroscopy. Comparing with pure ZnO nanofibers, Co-doped nanofibers exhibit improved acetone sensing properties at 360 °C. The response of 0.5 wt% Co-doped ZnO nanofibers to 100 ppm acetone is about 16, which is 3.5 times larger than that of pure nanofibers (about 4.4). The response and recovery times of 0.5 wt% Co-doped ZnO nanofibers to 100 ppm acetone are about 6 and 4 s, respectively. Moreover, Co-doped ZnO nanofibers can successfully distinguish acetone and ethanol/methanol, even in a complicated ambience. The high response and quick response/recovery are based on the one-dimensional nanostructure of ZnO nanofibers combining with the Co-doping effect. The selectivity is explained by the different optimized operating temperatures of Co-doped ZnO nanofibers to different gases.     

High-performance liquefied petroleum gas sensing based on nanostructures of zinc oxide and zinc stannate

Toxic and combustible gas detection plays a major role in environmental air quality monitoring. Real-time monitoring of hazardous gases and signal of accidental leakages is of great importance owing to the concern for safety requirements in industries and household applications. A simple and economical method for the fabrication of highly sensitive zinc oxide (ZnO) nanorods based gas sensors for detecting low concentrations of Liquefied Petroleum Gas (LPG) was studied in this work. Platinum (Pt) nanoparticles were deposited on the sensing medium which acts as catalysts to improve the sensor performance. The change in electrical resistance of the metal oxide semiconductor for varying concentrations of LPG was measured. Maximum response of 59% was achieved for 9000 ppm LPG at 250 °C. Further to improve the sensing performance of the sensor towards LPG, surface modification of ZnO nanorods using zinc stannate (Zn₂SnO₄) microcubes was performed. High response of 63% was observed for 3000 ppm LPG at 250 °C. Significant improvement in response of the sensor with Zn₂SnO₄ microcubes on ZnO nanorods was observed when compared to sensor with ZnO nanorods.     

Selectivity of flame-spray-made Nb/ZnO thick films towards NO2 gas

Unloaded ZnO and Nb/ZnO nanoparticles containing 0.25, 0.5 and 1 mol.% Nb were produced in a single step by flame-spray pyrolysis (FSP) technique. The nanoparticles were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The BET surface area (SSA_BET) of the nanoparticles was measured by nitrogen adsorption. FSP yielded small Nb particles attached to the surface of the supporting ZnO nanoparticles, indicating a high SSA_BET. The morphology and accurate size of the primary particles were further investigated by TEM. Nb/ZnO nanoparticles paste composed of ethyl cellulose and terpineol as binder and solvent respectively was coated on Al₂O₃ substrate interdigitated with gold electrodes to form thick films by spin coating technique. After the sensing tests, the morphology and the cross-section of sensing film were analyzed by SEM and EDS analyses. The influence on a low dynamic range of Nb concentration on NO₂ response (0.1-4 ppm) of thick film sensor elements was studied at the operating temperatures ranging from 250 to 350 °C in the presence of dry air. The optimum Nb concentration was found be 0.5 mol.% and 0.5 mol.% Nb exhibited an optimum NO₂ response of ∼1640 and a short response time (27 s) for NO₂ concentration of 4 ppm at 300 °C.     

Improving the ethanol sensing of ZnO nano-particle thin films—The correlation between the grain size and the sensing mechanism

ZnO and Sn doped ZnO (ZnO:Sn) thin films at various doping concentrations from 1 to 10 at.% were prepared by the sol-gel method for an ethanol sensing application. The Sn doping significantly influenced the film growth, grain size and response of the films. The XRD patterns showed that the hexagonal wurtzite structure of the ZnO film was retained even after the Sn doping. The crystallite grain sizes of the ZnO:Sn thin films at 0, 2 and 4 at.% were estimated by using the typical Scherrer's equation. The crystalline quality of the films at 6, 8 and 10 at.% of Sn was degenerated. Typical FESEM images demonstrated the different morphologies for the ZnO:Sn thin films at various Sn concentrations; many pores of various dimensions were observed depending on the doping level. A TEM analysis of the ZnO:Sn thin films at 0, 2 and 4 at.% was performed to verify the grain size. The optimum Sn doping level of ZnO:Sn thin film for ethanol sensing was estimated to be 4 at.%. The 4 at.% sample obtained the highest response to ethanol vapor in the 10-400 ppm level range at a low operating temperature of 250 °C. The sensing mechanism was explained by a variation in the sensitivity model from a neck-grain-boundary controlled sensitivity to a neck-controlled sensitivity. Our work demonstrates the ability to reduce the working temperature as well as to increase the response of ZnO thin film based gas sensors to detect ethanol, which would be of great merit for commercialized applications.     

Formaldehyde sensing properties of electrospun NiO-doped SnO2 nanofibers

Formaldehyde is a kind of hazardous gases dangerous to human health. Hence, gas sensor is an essential device to monitor formaldehyde in air, especially in indoor ambient. Semiconductor metal oxides are studied as gas-sensing material to detect most of key gases for decade years. For the purpose of actual application and meeting a variety of conditions, diverse additives added into host material are expected to improve the performance of gas sensors. The formaldehyde gas-sensing characteristics of undoped and NiO-doped SnO₂ (NSO) nanofibers synthesized via a simple electrospinning method were investigated in this study. It is noticed that the addition of NiO causes the distortion at the surface of SnO₂ nanofibers, which is responsible to adjust activation energy, grain sizes and chemical states of host material. The sensors fabricated from NSO nanofibers exhibited good formaldehyde sensing properties at operating temperature 200 °C, and the minimum-detection-limit was down to 0.08 ppm. The response time and recovery time of the sensors were about 50 s and 80 s to 10 ppm formaldehyde, respectively. The sensor shows a good long-term stability in 90 days. The simple preparation and excellent properties significantly advance the viability of electrospun nanofibers as gas sensing materials. The sensing mechanisms of NSO nanofibers to formaldehyde were discussed. The results indicated that NSO nanofibers could be used as a candidate to fabricate formaldehyde sensors in practice.     

Synthesis of quantum size ZnO crystals and their gas sensing properties for NO2

Quantum size ZnO crystals have been synthesized successfully by a room temperature sol-gel process. Oleic acid (OA) has been used as capping agent to control the particle size of ZnO. The crystal structure and size of the ZnO are characterized by the X-ray diffraction (XRD) and transmission electron microscope (TEM). The XRD results show the as-synthesized ZnO has hexagonal wurtzite structure and the average crystallite size is 5.7 nm which is little less than TEM result. It is testified by photoluminescence (PL) and Raman spectra that the quantum size ZnO keeps the crystal structure of the bulk ZnO and possesses more surface defects. The quantum size ZnO has the highest response of 280 to NO₂ and the highest selectivity of 31 and 49 corresponding to CO and CH₄ at operating temperature of 290 °C. The effect of calcination temperatures on sensing property and transient response of the ZnO sensor are also investigated.     

Nanostructured spinel ZnCo2O4 for the detection of LPG

Nanostrucutred spinel ZnCo₂O₄ (∼26-30 nm) was synthesized by calcining the mixed precursor (consisting of cobalt hydroxyl carbonate and zinc hydroxyl carbonate) in air at 600 °C for 5 h. The mixed precursor was prepared through a low cost and simple co-precipitation/digestion method. The transformation of the mixed precursor into nanostructured spinel ZnCo₂O₄ upon calcinations was confirmed by X-ray diffraction (XRD) measurement, thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS) and high resolution transmission electron microscopy (HRTEM). To demonstrate the potential applicability of ZnCo₂O₄ spinel in the fabrication of gas sensors, its LPG sensing characteristics were systematically investigated. The ZnCo₂O₄ spinel exhibited outstanding gas sensing characteristics such as, higher gas response (∼72-50 ppm LPG gas at 350 °C), response time (∼85-90 s), recovery time (∼75-80 s), excellent repeatability, good selectivity and relatively lower operating temperature (∼350 °C). The experimental results demonstrated that the nanostructured spinel ZnCo₂O₄ is a very promising material for the fabrication of LPG sensors with good sensing characteristics. Plausible LPG sensing mechanism is also discussed.     

Acetylene sensor based on Pt/ZnO thick films as prepared by flame spray pyrolysis

ZnO nanoparticles loaded with 0.2-2.0 at.% Pt have been successfully produced in a single step by flame spray pyrolysis (FSP) technique using zinc naphthenate and platinum(II) acetylacetonate, as precursors dissolved in xylene and their acetylene sensing characteristics have been investigated. The particle properties were analyzed by XRD, BET, TEM, SEM and EDS. Under the 5/5 (precursor/oxygen) flame condition, ZnO nanoparticles and nanorods were observed. The crystallite sizes of ZnO spherical and hexagonal particles were found to be ranging from 5 to 20 nm while ZnO nanorods were seen to be 5-20 nm in width and 20-40 nm in length. In addition, very fine Pt nanoparticles with diameter of ∼1 nm were uniformly deposited on the surface of ZnO particles. From gas-sensing characterization, acetylene sensing characteristics of ZnO nanoparticles is significantly improved as Pt content increased from 0 to 2  at.%. The 2 at.% Pt loaded ZnO sensing film showed an optimum C₂H₂ response of ∼836 at 1% acetylene concentration and 300 °C operating temperature. A low detection limit of 50 ppm was obtained at 300 °C operating temperature. In addition, Pt loaded ZnO sensing films exhibited good selectivity towards hydrogen, methane and carbon monoxide.     

Fabrication and gas-sensing properties of hierarchically porous ZnO architectures

Hierarchically three-dimensional (3D) porous ZnO architectures are synthesized by a template-free, economical aqueous solution method combined with subsequent calcination. First, the precursors of interlaced and monodisperse basic zinc nitrate (BZN) nanosheets are prepared. Then calcination of the precursors produces hierarchically 3D porous ZnO architectures composed of interlaced ZnO nanosheets with high porosity resulting from the thermal decomposition of the precursors. The products are characterized by X-ray diffraction, thermogravimetric-differential thermalgravimetric analysis, scanning electron microscopy, transmission electron microscopy, and Brunauer-Emmett-Teller N₂ adsorption-desorption analyses. The BET surface area of the hierarchically porous ZnO nanostructures was calculated to be 12.8 m² g⁻¹. Compared with ZnO rods, the as-prepared porous ZnO nanosheets exhibit a good response and reversibility to some organic gases, such as ethanol and acetone. The responses to 100 ppm ethanol and acetone are 24.3 and 31.6, respectively, at a working temperature of 320 °C. These results show that the porous ZnO architectures are highly promising for gas sensor applications, as the gas diffusion and mass transportation in sensing materials are significantly enhanced by their unique structures. Moreover, it is believed that this solution-based approach can be extended to fabricate other porous metal oxide materials with a unique morphology or shape.     

Synthesis of ZnO nanorods and its application in NO2 sensors

One-dimensional (1D) ZnO nanorods with pencil-like shape and high aspect ratio were successfully synthesized using a cetyltrimethylammonium bromide (CTAB)-assisted hydrothermal process at 90 °C. The surface morphology and structure of nanocrystals were characterized by FE-SEM, XRD and XPS analysis. Experimental results show that the surfactant and base concentration play important roles in the formation and growth orientation of ZnO nanorods. The ZnO nanorods synthesized exhibits high response and selectivity to NO₂, the highest response to 40 ppm NO₂ reached 206 and the selectivity with respect to CO and CH₄ at same concentration reached 10.3 and 30 times, respectively. The effects of synthesis method, surfactant and calcination condition on sensing properties were systematically investigated. The results indicate that the CTAB-assisted low temperature hydrothermal process is a potentially facile method for synthesis of 1D ZnO nanorods and excellent potential candidates as gas sensing materials.     

Fabrication of N-type Fe2O3 and P-type LaFeO3 nanobelts by electrospinning and determination of gas-sensing properties

N-type Fe₂O₃ nanobelts and P-type LaFeO₃ nanobelts were prepared by electrospinning. The structure and micro-morphology of the materials were characterized by X-ray diffraction (XRD) and scanning of electron microscopy (SEM). The gas sensing properties of the materials were investigated. The results show that the optimum operating temperature of the gas sensors fabricated from Fe₂O₃ nanobelts is 285 °C, whereas that from LaFeO₃ nanobelts is 170 °C. Under optimum operating temperatures at 500 ppm ethanol, the response of the gas sensors based on these two materials is 4.9 and 8.9, respectively. The response of LaFeO₃-based gas sensors behaves linearly with the ethanol concentration at 10-200 ppm. Sensitivities to different gases were examined, and the results show that LaFeO₃ nanobelts exhibit good selectivity to ethanol, making them promising candidates as practical detectors of ethanol.     

Highly sensitive and selective LPG sensor based on α-Fe2O3 nanorods

The α-Fe₂O₃ nanorods were successfully synthesized without any templates by calcining the α-FeOOH precursor in air at 300 °C for 2 h and their LPG sensing characteristics were investigated. The α-FeOOH precursor was prepared through a simple and low cost wet chemical route at low temperature (40 °C) using FeSO₄·7H₂O and CH₃COONa as starting materials. The formation of α-FeOOH precursor and its topotactic transformation to α-Fe₂O₃ upon calcination was confirmed by X-ray diffraction measurement (XRD), X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM) analysis. The α-Fe₂O₃ nanorods exhibited outstanding gas sensing characteristics such as, higher gas response (∼1746-50 ppm LPG at 300 °C), extremely rapid response (∼3-4 s), relatively slow recovery (∼8-9 min), excellent repeatability, good selectivity and lower operating temperature (∼300 °C). Furthermore, the α-Fe₂O₃ nanorods are able to detect up to 5 ppm for LPG with reasonable response (∼15) at the operating temperature of 300 °C and they can be reliably used to monitor the concentration of LPG over the range (5-60 ppm). The experimental results clearly demonstrate the potential of using the α-Fe₂O₃ nanorods as sensing material in the fabrication of LPG sensors. Plausible LP G sensing mechanism of the α-Fe₂O₃ nanorods is also discussed.     

Facile synthesis of hierarchical SnO2 semiconductor microspheres for gas sensor application

Hierarchical SnO₂ microspheres were synthesized by a hydrothermal method at 140 °C using stannic chloride hydrate and sodium hydroxide as starting materials. The individual hierarchical SnO₂ microsphere ranged from 700 to 900 nm in diameter. After these microspheres were heated at 600 °C for 2 h, the spheres were cross-linked into clusters by short SnO₂ nanorods as revealed by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). Most importantly, SnO₂ hierarchical microsphere sensor exhibits excellent selectivity and fast response to ethanol. Response and recovery times were 0.6 s and 11 s when the sensor was exposed to 50 ppm ethanol at an operating temperature of 300 °C. Thus, hierarchical structures play a significant role in the field of gas sensing.     

Effect of aluminium doping on structural and gas sensing properties of zinc oxide thin films deposited by spray pyrolysis

A facile spray pyrolysis route is used to deposit aluminium doped ZnO (AZO) thin films on to the glass substrates. It is observed that on aluminium doping the particle size of ZnO reduces significantly; moreover, uniformity of particle also gets enhanced. Their XRD study reveals that intensity ratio of crystal planes depend on the aluminium doping concentration. The gas response studies of; ∼800 nm thick Al-doped ZnO films at different operating temperatures show that 5 at% Al-doped ZnO thin film exhibits highest response towards H₂S gas at 200 °C. The results suggest that the gas response strongly depends on the particle size and aluminium doping in the ZnO.     

Synthesis and characterisation of nanosized TiO2-ZrO2 binary system prepared by an aqueous sol-gel process: Physical and sensing properties

Nanostructured TiO₂-ZrO₂ thin films and powders were prepared by a straightforward aqueous particulate sol-gel route. Titanium (IV) isopropoxide and zirconium (IV) acetate hydrate were used as precursors, and hydroxypropyl cellulose was used as a polymeric fugitive agent in order to increase the specific surface area. X-ray diffraction (XRD) and Fourier transform infrared (FTIR) spectroscopy revealed that the powder were crystallised at the low temperature of 500 °C, containing anatase-TiO₂ and tetragonal-ZrO₂ phases. Furthermore, it was found that ZrO₂ retarded the anatase-to-rutile transformation up to 900 °C. The activation energies for crystallite growth of TiO₂ and ZrO₂ components in the binary system were calculated 10.16 and 3.12 kJ/mol, respectively. Transmission electron microscope (TEM) image showed that one of the smallest crystallite sizes was obtained for TiO₂-ZrO₂ binary mixed oxide, being 5 nm at 500 °C. Field emission scanning electron microscope (FESEM) analysis revealed that the deposited thin films had nanostructured morphology with the average grain size of 20 nm at 500 °C and 36 nm at 900 °C. Thin films produced under optimised conditions showed excellent microstructural properties for gas sensing applications. They exhibited a remarkable response towards low concentrations of CO and NO₂ gases at low operating temperature of 150 °C, resulted in an increase of thermal stability of sensing films as well as a decrease in the power consumption. Furthermore, calibration curves revealed that TiO₂-ZrO₂ sensor follows the power law, S = A[gas]^B (where S is sensor response, coefficients A and B are constants and [gas] is gas concentration) for the two types of gases, and it has excellent capability for the detection of low gas concentrations.     

LPG sensing properties of Pd-sensitized vertically aligned ZnO nanorods

One-dimensional (1-D) vertically aligned ZnO nanorods are synthesized on glass substrate through a simple chemical route and their liquefied petroleum gas (LPG) sensing properties are studied. The morphology and structure of vertically aligned ZnO nanorods has been characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD) analysis. The LPG sensing properties of the vertically aligned ZnO nanorods are improved significantly after palladium (Pd) sensitization. The unsensitized vertically aligned ZnO nanorods exhibited the maximum response of 37% at 573 K upon exposure to 2600 ppm LPG, which improved to 60% at operating temperature of 498 K after the Pd sensitization. The Pd-sensitized vertically aligned ZnO nanorods showed more selectivity towards LPG as compared to CO₂. Our results demonstrate that the chemically grown vertically aligned ZnO nanorods along with Pd sensitization are promising material for the fabrication of cost effective and high performance gas sensors.     

Carbon dioxide sensing properties of bismuth cobaltite

Bismuth cobaltite with sillenite-type structure was prepared from Co(OH)₂ and Bi(NO₃)₃·6H₂O through solid state reaction at 600 °C. Neutron powder diffraction (NPD) data and X-ray absorption spectroscopy revealed the existence of mixed oxidation states for cobalt in this compound, the chemical formula being Bi₁₂(Bi_0.55Co_0.45)O_19.6. The gas sensing properties of Bi₁₂(Bi_0.55Co_0.45)O_19.6 were characterized by alternating current, at 200, 300 and 400 °C. The optimal response was observed at 400 °C, using a frequency of 100 kHz.     

Enhanced H2S sensing characteristics of Pt doped SnO2 nanofibers sensors with micro heater

Gas sensors were designed and fabricated using oxide nanofibers as the sensing materials on micro platforms using micromachining technology. Pure and Pt doped SnO₂ nanofibers were prepared by electrospinning and their H₂S gas sensing characteristics were subsequently investigated. The sensing temperatures of 300 and 500 °C could be attained at the heater powers of 36 and 94 mW, respectively, and the sensors showed high and fast responses to H₂S. The responses of 0.08 wt% Pt doped SnO₂ nanofibers to 4-20 ppm H₂S, were 25.9-40.6 times higher than those of pure SnO₂ nanofibers. The gas sensing characteristics were discussed in relation to the catalytic promotion effect of Pt, nano-scale morphology of electrospun nanofibers, and sensor platform using micro heater.