Characterization and gas sensing properties of bead-like ZnO using multi-walled carbon nanotube templates

We report bead-like ZnO nanostructures for gas sensing applications, synthesized using multi-walled carbon nanotube (MWCNT) templates. The ZnO nanostructures are grown following a two-step process: in the first, ZnO nanoparticles are synthesized on MWCNTs by thermal evaporation of a Zn powder; and in the second, the hybrid nanostructures are heat-treated at 800 °C. Scanning and transmission electron microscopy images indicate that the bead-like ZnO nanostructures have surface protuberances with nanoparticle sizes ranging from 20 to 60 nm, and a well-crystallized hexagonal structure. Gas sensors based on multiple-networked bead-like ZnO showed considerably enhanced electrical responses and better stability to both oxidizing (NO₂) and reducing (CO) gases compared with previously reported nanostructured gas sensors, even if the response to CO gas was slow to increase. Both the NO₂ and CO gas sensing properties increased dramatically when the working temperature was increased up to 300 °C. The response sensitivities measured were 2953%, 5079%, 9641%, 3568%, and 3777% to 20 ppm NO₂ at 200, 250, 300, 350 and 400 °C, respectively. For CO gas on the other hand, the response sensitivities were 107%, 110%, 114%, 118%, and 122% at 5, 10, 20, 50, and 100 ppm concentrations, respectively. For concentrations between 5 and 20 ppm, the recovery time of the oxidizing gas was much shorter than the response time. The origin of the NO₂/CO gas sensing mechanism of the bead-like ZnO nanostructures is discussed.     

Hydrogen-sensing response of grass-like carbon nanotube/nickel nanostructure by microwave treatment

A grass-like carbon nanotube/nickel (CNT/Ni) sensor treated by microwave (MW) technique to enhance hydrogen (H₂) gas-sensing response was used. A leaf-like CNT/Ni nanostructure was changed into a grass-like CNT/Ni nanostructure through the MW treatment technique in order to enhance the H₂ sensor response. The H₂ gas sensing characteristics of grass-like CNT/Ni were found to have a much higher sensor response of ∼11% at 1000 ppm H₂ gas, approximately 33 times greater than that of leaf-like CNT/Ni (∼0.33%) without MW treatment. The MW technique is simple, energy-efficient at low temperature (58 °C), and effectively enhances the sensing response of CNT/Ni sensors.     

ZnO-capped nanorod gas sensors

This paper reports on the synthesis of pristine α-Fe₂O₃ nanorods and Fe₂O₃–ZnO core–shell nanorods using a combination of thermal oxidation and atomic layer deposition (ALD) techniques; the completed nanorods were then used for ethanol sensing studies. The crystal structure and morphology of the synthesized nanostructures were examined by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The sensing properties of the pristine and core–shell nanorods for gas-phase ethanol were examined using different concentrations of ethanol (5–200 ppm) at different temperatures (150–250 °C). The XRD and SEM revealed the excellent crystallinity of the Fe₂O₃–ZnO core–shell nanorods, as well as their uniformity in terms of shape and size. The Fe₂O₃–ZnO core–shell nanorod sensor showed a stronger response to ethanol than the pristine Fe₂O₃ nanorod sensor. The response (i.e., the relative change in electrical resistance R_a/R_g) of the core–shell nanorod sensor was 22.75 for 100 ppm ethanol at 200 °C whereas that of the pristine nanorod sensor was only 3.85 under the same conditions. Furthermore, under these conditions, the response time of the Fe₂O₃–ZnO core–shell nanorods was 15.96 s, which was shorter than that of the pristine nanorod sensor (22.73 s). The core–shell nanorod sensor showed excellent selectivity to ethanol over other VOC gases. The improved sensing response characteristics of the Fe₂O₃–ZnO core–shell nanorod sensor were attributed to modulation of the conduction channel width and the potential barrier height at the Fe₂O₃–ZnO interface accompanying the adsorption and desorption of ethanol gas as well as to preferential adsorption and diffusion of oxygen and ethanol molecules at the Fe₂O₃–ZnO interface.     

Aqueous chemical route deposition of nanocrystalline ZnO thin films as acetone sensor: Effect of molarity

Nanocrystalline ZnO thin films were deposited onto glass substrate using a simple and inexpensive aqueous chemical method at low temperature (90 °C). The concentration of precursor solution was varied in order to study its effect on structural, morphological, and gas response properties. Field-emission scanning electron microscopy (FESEM) images indicate the growth of ZnO with hexagonal shaped nanostructure. Further these films were used to explore gas response properties towards acetone, propanol and ethanol vapors. The sensor response was found to be decreased with increase in precursor concentration. The highest sensor response of 92% was observed towards acetone for the film deposited at 0.05 M at an operating temperature of 350 °C. The higher vapor response towards acetone is attributed to size and surface morphology of the film deposited at 0.05 M.     

Transparent gas senor and photodetector based on Al doped ZnO nanowires synthesized on glass substrate

In this work high density, well-aligned Al doped ZnO (AZO) nanowires are hydrothermally synthesized on glass substrate at 99 °C. The Al content is ~1.57 at%. The PL spectrum shows that Al impurities caused an increase in the number of oxygen vacancies. The spectral response results show that the maximum responsivity and quantum efficiencies η of AZO NWs are 3.61 A/W and 84.9%, at an incident light wavelength of 360 nm. These AZO NWs have less humidity sensitivity, thus decreasing the effect of humidity effect on gas sensing. Low gas concentrations of 10 ppm ethanol and 10 ppm acetone can be detected with good responses of 24.5% and 21.2%, using the AZO NW sensor at 200 °C and with 0.1 V applied bias.     

Synthesis,characterization and acetone gas sensing applications of Ag-doped ZnO nanoneedles

Herein, we report the simple synthesis, characterization and acetone gas sensing applications of Ag-doped ZnO nanoneedles prepared by facile hydrothermal method. The synthesized nanoneedles were characterized through different characterization techniques to examine its crystallinity, phase structure, morphological, compositional, optical, vibrational and gas sensing properties. The detailed morphological studies revealed that the Ag-doped ZnO nanoneedles are assembled into non-homogeneously distributed flower-shaped structures which are grown in high density. Further characterizations confirmed that the synthesized nanoneedles are pure, possessing well-crystallinity and exhibiting good optical and vibrational properties. The synthesized Ag-doped ZnO nanoneedles were used as functional material to fabricate high sensitive acetone gas sensors. The effect of operating temperature and concentration of the acetone were analyzed for detailed sensing performance of synthesized nanoneedles. By detailed sensing experiments, the response and recovery times of 10 s and 21 s, respectively were calculated at acetone concentration of 100 ppm at an optimized operating temperature of 370 °C. A maximum sensitivity of 30.233 was recorded at 370 °C operating temperature for 200 ppm of acetone for the fabricated acetone sensor based on Ag-doped ZnO nanoneedles.     

Dispersant-assisted low frequency electrophoretically deposited TiO2 nanoparticles in non-aqueous suspensions for gas sensing applications

The effect of dispersant on deposition mechanism of TiO₂ nanoparticles at 1 Hz under non-uniform AC fields was investigated. It was found that by adding Dolapix to suspension, deposition pattern is drastically changed enabling particles to enter the gap leaving the electrodes intact. Using low frequency AC electrophoretic deposition technique in the presence of dispersant, we succeeded in fabricating gas sensor in less than 2 min. Gas sensing measurements were performed in the temperature range of 450–550 °C. The results explained that the sensor has good stability in time and repeatability performance toward high response. The maximum sensitivity of about 180 for the TiO₂ nanoparticles sensor is observed with 47 ppm NO₂ gas and the response and recovery times is about 60–150 s. The optimum temperature of the gas sensor was obtained in 450 °C where sensor showed a linear trend up to 50 ppm of NO₂ gas. This sensing behavior in un-doped TiO₂ as NO₂ sensor can be mainly ascribed to the porous structure of the sensing film and its good contacts to the substrate and electrode assembly.     

Enhanced performance of γ-Fe2O3:WO3 nanocomposite towards selective acetone vapor detection

Metal oxide nanocomposite sensors based on γ-Fe₂O₃ and WO₃ were investigated in acetone vapor of various concentrations (1–100 ppm) at operating temperatures between 250 and 350 °C. The composites were prepared by simple solid state mixing and porous thick-film gas sensors were fabricated on alumina substrates. The γ-Fe₂O₃:WO₃ (50:50) nanocomposite showed a marked enhancement in sensing response down to 1 ppm acetone vapor detection at 300 °C. The response was ~2-fold better compared to pure WO₃ or pure γ-Fe₂O₃ with a very fast response (1 s) and very short recovery time (3 s). No appreciable sensitivity was observed towards alcohol vapor (an interfacing agent for diabetics) and in moisture (present in breath). The enhanced performance was due to n–n heterojunction effect.     

Nanostructured nickel ferrite: A liquid petroleum gas sensor

The present investigation deals with the synthesis of nanostructured nickel ferrite (NiFe₂O₄) and their liquid petroleum gas-sensing characteristics. The 15–20 nm size nickel ferrite has been synthesized at 700 °C by a simple molten-salt route using sodium chloride as grain growth inhibitor. These nanoparticles exhibit significantly high response towards liquid petroleum gas (LPG) in comparison with ethanol vapor, hydrogen sulfide, ammonia and hydrogen. The gas response towards various gases at their 200 ppm concentrations is investigated at 200–450 °C. Different characterization techniques have been employed, such as differential thermal analysis, X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and high resolution transmission electron microscopy (HRTEM) to study the crystallite size, structure and morphology. The results suggest possibility of utilization of the nanostructured nickel ferrite, without addition of any precious metal ion, as the LPG detector.     

Tin–Zinc oxide composite ceramics for selective CO sensing

Composite metal oxide gas sensors were intensely studied over the past years having superior performance over their individual oxide components in detecting hazardous gases. A series of pellets with variable amounts of SnO₂ (0–50 mol%) was prepared using wet homogenization of the component oxides leading to the composite tin-zinc ceramic system formation. The annealing temperature was set to 1100 °C. The samples containing 2.5 mol% SnO₂ and 50 mol% SnO₂ were annealed also at 1300 °C, in order to observe/to investigate the influence of the sintering behaviour on CO detection. The sensor materials were morphologically characterized by scanning electron microscopy (SEM). The increase in the SnO₂ amount in the composite ceramic system leads to higher sample porosity and an improved sensitivity to CO. It was found that SnO₂ (50 mol%) - ZnO (50 mol%) sample exhibits excellent sensing response, at a working temperature of 500 °C, for 5 ppm of CO, with a fast response time of approximately 60 s and an average recovery time of 15 min. Sensor selectivity was tested using cross-response to CO, methane and propane. The results indicated that the SnO₂ (50 mol%)-ZnO (50 mol%) ceramic compound may be used for selective CO sensing applications.     

Synthesis,characterization and enhanced acetone sensing performance of Pd loaded Sm doped SnO2 nanoparticles

In the present communication, we have presented a high performance acetone sensor based on Pd loaded Sm doped SnO₂ nanomaterial. The (0.5, 1, 2 and 3) wt% Pd loaded 6 mol% Sm doped SnO₂ nanoparticles were prepared using a co-precipitation method. The characterization of samples was done by using X-ray diffraction (XRD), Field Emission Scanning Electron Microscopy (FEG-SEM), Energy Dispersive Analysis by X-rays (EDAX), High Resolution-Transmission Electron Microscopy (HR-TEM) and Selective Area Electron Diffraction (SAED) techniques. The gas response studies such as sensitivity, selectivity and stability towards liquid petroleum gas, ammonia, ethanol and acetone were measured at 100 ppm concentrations. The results show that optimum Pd loading (2 wt%) results in smaller crystallite size (~3.1 nm), lower operating temperature (200 °C), higher gas response (94%),better selectivity, faster response (~3 s) and quicker recovery (~12 s) towards acetone.     

The O2-dependent growth of ZnO nanowires and their photoluminescence properties

ZnO nanowires were massively synthesized on a Ni(NO₃)₂-coated silicon substrate under oxygen-containing argon atmosphere by a simple chemical vapor deposition method. The average diameter of the ZnO nanowires was about 50 nm and the average length was about 20 μm. The morphologies of the ZnO nanowires strongly depended on oxygen content in the growth atmosphere. At low oxygen concentration (about 5–10 ppm), ZnO nanocones and nanoneedles were obtained, while at high oxygen concentration (about ∼250 ppm), ZnO nanoparticles deposited on the substrate. The room temperature photoluminescence (PL) spectrum of the ZnO nanowires revealed that a strong UV band at 384 nm dominated the whole spectrum. These results indicate that the ZnO nanowires grown under oxygen-containing atmosphere possess better crystalline quality and UV luminescence properties than those grown in reducing hydrogen atmosphere. Based on the analysis of oxygen effect on the ZnO nanostructures, a vapor–liquid–solid mechanism assisted by the redox growth mode was proposed to understand the growth of the ZnO nanowires.     

Nanostructured perovskite oxides – LaMO3 (M=Al,Co, Fe) prepared by co-precipitation method and their ethanol-sensing characteristics

Nanostructured La-based perovskite oxides − LaMO₃ (M=Al, Co, Fe) were synthesized by a new co-precipitation procedure using metal nitrate and carbonate salts as starting materials. X-ray diffraction and energy dispersive X-ray spectroscopic results confirmed the formation of single-phase nanocrystalline perovskite oxides with high purity. Characterizations by scanning/transmission electron microscopy and nitrogen adsorption revealed that LaAlO₃ was produced in the form of rectangular porous nanorods exhibiting much larger surface area and porosity compared with densely aggregated LaCoO₃ particles and loosely clustered LaFeO₃ nanoparticles with cracked-egg morphologies. The materials were characterized for gas sensing towards ethanol at 200–350 °C. From gas-sensing results, the LaAlO₃ sensor displayed n-type gas-sensing behaviors with considerably higher ethanol response than p-type LaFeO₃ and LaCoO₃ sensors, respectively. In particular, the LaAlO₃ sensor exhibited a high response of 16.45–1000 ppm ethanol and excellent ethanol selectivity against NO₂, SO₂, CO and H₂ at 350 °C. The superior gas-sensing performances could be attributed to the effective receptor function, transducer function and utility factor of LaAlO₃ nanorod structures prepared by the co-precipitation method.     

Highly responsive hydrogen gas sensing by partially reduced graphite oxide thin films at room temperature

Novel chemo-resistive gas sensors based on reduced graphite oxide (rGO) thin films have been fabricated and evaluated for hydrogen detection. The rGO materials were thermally treated at various conditions and analyzed using X-ray diffraction, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy techniques to investigate the change of functional groups. The semiconductor type of the rGOs treated at different conditions were checked by flowing hydrogen gas at 20 cm³/min (sccm) under 10 Torr partial pressure. The rGOs treated at 70 °C in atmosphere (rGO070a), 200 °C in a vacuum (rGO200v), and 500 °C in a vacuum (rGO500v) exhibited n-type, ambipolar, and p-type behavior, respectively. The rGO500v was adopted as active sensing element without any rare metal decoration, and its sensing response to hydrogen was studied by using air as carrier gas. The rGO500v exhibited good sensitivity (～4.5%), response time (～20 s), and recovery time (～10 s) to 160 ppm hydrogen gas at room temperature.     

CO removal from reformed fuel over Cu/ZnO/Al2O3 catalysts prepared by impregnation and coprecipitation methods

A composition of Cu/ZnO/Al₂O₃ catalysts prepared by the impregnation method was optimized for water gas shift reaction (WGSR) coupled with CO oxidation in the reformed gas. The optimum composition of the impregnated catalyst for high WGSR activity was 5 wt.% Cu/5 wt.% ZnO/Al₂O₃. The optimum loading amounts of Cu and ZnO in the impregnated catalyst were smaller than those in the coprecipitated catalyst. Its catalytic activity above 200 °C was comparable to that of the conventional coprecipitated Cu/ZnO/Al₂O₃ catalyst. However, the activity of the impregnated Cu/ZnO/Al₂O₃ catalysts was significantly lowered at 150 °C, whereas no deactivation was observed for the coprecipitated catalyst at the same temperature. It was found that deactivation occurred over impregnated catalysts with H₂O and/or O₂ in the reaction gas; it prevented CO adsorption on the surface.     

Enhanced NO2 sensing properties of Zn2SnO4-core/ZnO-shell nanorod sensors

Zn₂SnO₄-core/ZnO-shell nanorods were synthesized using a two-step process: synthesis of Zn₂SnO₄ nanorods the thermal evaporation of a mixture of ZnO, SnO₂, and graphite powders, followed by atomic layer deposition (ALD) of ZnO. The nanorods were 50–250 nm in diameter and a few to a few tens of micrometers in length. The cores and shells of the nanorods were face-centered cubic-structured single crystal Zn₂SnO₄ and wurtzite-structured single crystal ZnO, respectively. The multiple networked Zn₂SnO₄-core/ZnO-shell nanorod sensors showed a response of 173–498% to NO₂ concentrations of 1–5 ppm at 300 °C. These response values are 2–5 times higher than those of the Zn₂SnO₄ nanorod sensor over the same NO₂ concentration range. The NO₂ sensing mechanism of the Zn₂SnO₄core/ZnO-shell nanorods is discussed.     

Elucidation of hydrogen mobility in coal under reductive atmosphere using a tritium tracer method

Hydrogen exchange reaction of three Argonne coals (Illinois No. 6, Upper Freeport and Pocahontas #3) and Wandoan coal with tritiated gaseous hydrogen were performed at several temperatures. Hydrogen exchange reaction was performed in a flow reactor packed with 0.4 g of coal and 0.05 g of catalysts under the following conditions: pressure 15 kg/cm², temperature 200, 250, 300 °C, carrier gas H₂ or N₂ 5 ml/min. When a pulse of [³H]H₂ was introduced into a coal in H₂ carrier gas at several temperatures, the delay of [³H]H₂ pulse observed increased with increasing the reaction temperature and decreased with increasing coal rank. Further in the reaction of tritiated coals with gaseous hydrogen at constant temperature, the hydrogen exchange rate was estimated from the release rate of [³H]H₂. The apparent hydrogen exchange rate at 200 °C was higher than that at 250 °C. This shows that the hydrogen with low reactivity came to participate in the reaction at high temperature. When the reaction of tritiated coal with gaseous hydrogen was performed during heat treatment, one, two or three peaks of tritium concentration were observed in the outlet of the reactor depending on temperature (200, 250 or 300 °C, respectively) at which tritium was incorporated into coal initially. It was suggested that there were at least three kinds of hydrogen with different reactivity in coal.     

Improved photoluminescence emission and gas sensor properties of ZnO thin films

In this article, we report a comparative study of the influence of pressure-assisted (1.72 MPa) versus ambient pressure thermal annealing on both ZnO thin films treated at 330 °C for 32 h. The effects of pressure on the structural, morphological, optical, and gas sensor properties of these thin films were investigated. The results show that partial preferential orientation of the wurtzite-structure ZnO thin films in the [002] or [101] planes is induced based on the thermal annealing conditions used (i.e., pressure assisted or ambient pressure). UV–vis absorption measurements revealed a negligible variation in the optical -band gap values for the both ZnO thin films. Consequently, it is deduced that the ZnO thin films exhibit different distortions of the tetrahedral [ZnO₄] clusters, corresponding to different concentrations of deep and shallow level defects in both samples. This difference induced a variation of the interface/bulk-surface, which might be responsible for the enhanced optical and gas sensor properties of the pressure-assisted thermally annealed film. Additionally, pressure-assisted thermal annealing of the ZnO films improved the H₂ sensitivity by a factor of two.     

High performance Cu–ZnO/Pd-β catalysts for syngas to LPG

The catalytic performance of Cu–ZnO/Pd-β catalyst for syngas to LPG (Liquefied Petroleum Gas) has been investigated in this paper. The kind of zeolite, SiO₂/Al₂O₃ ratio in Pd-β, Pd-β particle size, Pd content in Pd-β, and reaction conditions, have been optimized. The results showed that the suitable reaction conditions for syngas to LPG over Cu–ZnO/Pd-β are: 325–350 °C, 2.1–3.6 MPa, 4.5–9 g h/mol gas velocity (W/F), and 37–75 ratio of SiO₂/Al₂O₃. At the optimal conditions, Cu–ZnO/Pd-β could exhibit an excellent catalytic performance for syngas to LPG: 72.2% CO conversion, 45.3% hydrocarbon yield and 78.0% LPG selectivity in hydrocarbons could be achieved.     

Characterization and optimization of an autothermal diesel and jet fuel reformer for 5 kWe mobile fuel cell applications

The present paper describes the characterization of an autothermal reformer designed to generate hydrogen by autothermal reforming (ATR) from commercial diesel fuel (～10 ppm S) and jet fuel (～200 ppm S) for a 5 kW_e polymer electrolyte fuel cell (PEFC). Commercial noble metal-based catalysts supported on 900 cpsi cordierite monoliths substrates were used for ATR with reproducible results. Parameters investigated in this study were the variation of the fuel inlet temperature, fuel flow and the H₂O/C and O₂/C ratios. Temperature profiles were studied both in the axial and radial directions of the reformer. Product gas composition was analyzed using gas chromatography.It was concluded from the experiments that an elevated fuel inlet temperature (≥60 °C) and a higher degree of fuel dispersion, generated via a single-fluid pressurized-swirl nozzle at high fuel flow, significantly improved the performance of the reformer. Complete fuel conversion, a reforming efficiency of 81% and an H₂ selectivity of 96% were established for ATR of diesel at P = 5 kW_e, H₂O/C = 2.5, O₂/C = 0.49 and a fuel inlet temperature of 60 °C. No hot-spot formation and negligible coke formation were observed in the reactor at these operating conditions. The reforming of jet fuel resulted in a reforming efficiency of only 42%. A plausible cause is the coke deposition, originating from the aromatics present in the fuel, and the adsorption of S-compounds on the active sites of the reforming catalyst.Our results indicate possibilities for the developed catalytic reformer to be used in mobile fuel cell applications for energy-efficient hydrogen production from diesel fuel.