Controlled synthesis and gas-sensing properties of hollow sea urchin-like α-Fe2O3 nanostructures and α-Fe2O3 nanocubes

Hollow sea urchin-like α-Fe₂O₃ nanostructures were successfully synthesized by a hydrothermal approach using FeCl₃ and Na₂SO₄ as raw materials, and subsequent annealing in air at 600 °C for 2 h. The hollow sea urchin-like α-Fe₂O₃ nanostructures with the diameters of 2–4.5 μm consist of well-aligned α-Fe₂O₃ nanorods with an average length of about 1 μm growing radially from the centers of the nanostructures, have a hollow interior with a diameter of about 2 μm. α-Fe₂O₃ nanocubes with a diameter of 700–900 nm were directly obtained by a hydrothermal reaction of FeCl₃ at 140 °C for 12 h. The response S_r (S_r = R_a/R_g) of the hollow sea urchin-like α-Fe₂O₃ nanostructures reached 2.4, 7.5, 5.9, 14.0 and 7.5 to 56 ppm ammonia, 32 ppm formaldehyde, 18 ppm triethylamine, 34 ppm acetone, and 42 ppm ethanol, respectively, which was excess twice that of the α-Fe₂O₃ nanocubes and the nanoparticle aggregations. Our results demonstrated that the hollow sea urchin-like α-Fe₂O₃ nanostructures were very promising for gas sensors for the detection of flammable and/or toxic gases with good-sensing characteristics.     

Preparation and characterization of nanocrystalline α-Fe2O3 by a sol-gel process

α-Fe₂O₃ ultra-fine powder with an average particle size of 6–26nm has been prepared by a sol-gel process. Thermal analysis, X-ray diffraction and transmission electron microscope were used to study its formation process and micro-structure. The temperature dependence of the electric conductance of the elements made of nanocrystalline α-Fe₂O₃ shows that the gas-sensing properties are strongly related to its surface. The elements exhibited good sensitivity and selectivity to ethyl alcohol, indicating it is a promising alcohol-sensing material.     

Solid-state potentiometric SO2 sensor combining NASICON with V2O5-doped TiO2 electrode

A compact tubular sensor based on NASICON (sodium super ionic conductor) and V₂O₅-doped TiO₂ sensing electrode was designed for the detection of SO₂. In order to reduce the size of the sensor, a thick-film of NASICON was formed on the outer surface of a small Al₂O₃ tube; furthermore, a thin layer of V₂O₅-doped TiO₂ with nanometer size was attached on the NASICON as a sensing electrode. This paper investigated the influence of V₂O₅ doping and sintering temperature on the characteristics of the sensor. The sensor attached with 5 wt% V₂O₅-doped TiO₂ sintered at 600 °C exhibited excellent sensing properties to 1–50 ppm SO₂ in air at 200–400 °C. The EMF value of the sensor was almost proportional to the logarithm of SO₂ concentration and the sensitivity (slope) was −78 mV/decade at 300 °C. It was also seen that the sensor showed a good selectivity to SO₂ against NO, NO₂, CH₄, CO, NH₃ and CO₂. Moreover, the sensor had speedy response kinetics to SO₂ too, the 90% response time to 50 ppm SO₂ was 10 s, and the recovery time was 35 s. On the basis of XPS analysis for the SO₂-adsorbed sensing electrode, a sensing mechanism involving the mixed potential at the sensing electrode was proposed.     

Nanoplates of α-SnWO4 and SnW3O9 prepared via a facile hydrothermal method and their gas-sensing property

Nanoplates of α-SnWO₄ and SnW₃O₉ were selectively synthesized in large scale via a facile hydrothermal reaction method. The final products obtained were dependent on the reaction pH and the molar ratio of W⁶⁺ to Sn²⁺ in the precursors. The as-prepared nanoplates of α-SnWO₄ and SnW₃O₉ were characterized by X-ray powder diffraction (XRD), N₂-sorption BET surface area, transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM) and X-ray photoelectron spectroscopy (XPS). The XPS results showed that Sn exists in divalent form (Sn²⁺) in SnW₃O₉ as well as in α-SnWO₄. The gas-sensing performances of the as-prepared α-SnWO₄ and SnW₃O₉ toward H₂S and H₂ were investigated. The hydrothermal prepared α-SnWO₄ showed higher response toward H₂ than that prepared via a solid-state reaction due to the high specific surface area. The gas-sensing property toward H₂S as well as H₂ over SnW₃O₉ was for the first time reported. As compared to α-SnWO₄, SnW₃O₉ exhibits higher response toward H₂S and its higher response can be well explained by the existence of the multivalent W (W⁶⁺/W⁴⁺) in SnW₃O₉.     

Tetrakis(alkylthio)-substituted lutetium bisphthalocyanines for sensing NO2 and O3

In this study, the nitrogen dioxide (NO₂) and ozone (O₃) sensing properties of a series bis[tetrakis(alkylthio) phthalocyaninato] lutetium(III) complexes [(C_nH_2n+1S)₄Pc]₂Lu(III) (n = 6, 10, 16) are investigated as a function of concentration in the temperature range between 25 °C and 150 °C. The concentration ranges were 1–10 ppm for NO₂, and 50 ppb–1 ppm for O₃. The response time and the sensor response to NO₂ are measured for approximately 1 min and 100% ppm⁻¹, respectively, for compound 1 at room temperature. At room temperature, all compounds are in the solid phase. The response time decreases to a few seconds with increasing operation temperature to 150 °C. At this temperature, all compounds are in the liquid crystal phase. The fastest response to oxidizing gases is observed at the liquid crystal phase of the Pcs. It has also been observed that the response time and the sensor response depend on the alkyl chain lengths of the Pcs. The doping effect of oxygen has been determined under high purity nitrogen N₂ flow, after exposure to dry air, at a different period of time and after annealing. It has been found that the conductivities of [(C_nH_2n+1S)₄Pc]₂Lu(III) thin films increased after exposure to dry air and the conduction mechanism also changed from ohmic behavior to space-charge-limited conduction.     

Plasma enhanced-CVD of undoped and fluorine-doped Co3O4 nanosystems for novel gas sensors

Co₃O₄-based nanosystems were prepared on polycrystalline Al₂O₃ by plasma enhanced-chemical vapor deposition (PE-CVD), at temperatures ranging between 200 and 400 °C. The use of two different precursors, Co(dpm)₂ (dpm = 2,2,6,6-tetramethyl-3,5-heptanedionate) and Co(hfa)₂·TMEDA (hfa = 1,1,1,5,5,5-hexafluoro-2,4-pentanedionate; TMEDA = N,N,N′,N′-tetramethylethylenediamine) enabled the synthesis of undoped and fluorine-doped Co₃O₄ specimens, respectively. A thorough characterization of their properties was performed by glancing incidence X-ray diffraction (GIXRD), atomic force microscopy (AFM), field emission-scanning electron microscopy (FE-SEM), secondary ion mass spectrometry (SIMS) and X-ray photoelectron spectroscopy (XPS). For the first time, the gas sensing properties of such PE-CVD nanosystems were investigated in the detection of ethanol and acetone. The results show an appreciable response improvement upon doping and functional performances directly dependent on the fluorine content in the Co₃O₄ system.     

Studies on the gas sensing behaviour of nanosized CuNb2O6 towards ammonia, hydrogen and liquefied petroleum gas

Appreciable changes in resistance of polycrystalline nanosized CuNb₂O₆ upon exposure to reducing gases like hydrogen, liquefied petroleum gas (LPG) and ammonia in ambient atmosphere recognize the material as a gas sensor. Nanosized CuNb₂O₆ synthesized by thermal decomposition of an aqueous precursor solution containing copper nitrate, niobium tartrate and tri-ethanol amine (TEA), followed by calcination at 700 °C for 2 h, has been characterized using X-ray diffraction (XRD) study, transmission electron microscopy (TEM), field-emission scanning electron microscope (FESEM), energy dispersive X-ray (EDX) analysis and Brunauer–Emmett–Teller (BET) surface area measurement. The synthesized CuNb₂O₆ exhibits monoclinic structure with crystallite size of 25 nm, average particle size of 25–40 nm and specific surface area of 55 m² g⁻¹.     

A route to high sensitivity and rapid response Nb2O5-based gas sensors: TiO2 doping, surface embossing, and voltage optimization

We report a novel route for the fabrication of highly sensitive and rapidly responding Nb₂O₅-based thin film gas sensors. TiO₂ doping of Nb₂O₅ films is carried out by co-sputtering without the formation of secondary phases and the surface area of TiO₂-doped Nb₂O₅ films is increased via the use of colloidal templates composed of sacrificial polystyrene beads. The gas sensitivity of Nb₂O₅ films is enhanced through both the TiO₂ doping and the surface embossing. An additional enhancement on the gas sensitivity is obtained by the optimization of the bias voltage applied between interdigitated electrodes beneath Nb₂O₅-based film. More excitingly, such a voltage optimization leads to a substantial decrease in response time. Upon exposure to 50 ppm CO at 350 °C, a gas sensor based on TiO₂-doped Nb₂O₅ film with embossed surface morphology exhibits a very high sensitivity of 475% change in resistance and a rapid response time of 8 s under 3 V, whereas a sensor based on plain Nb₂O₅ film shows a 70% resistance change and a response time of 65 s under 1 V. Thermal stability tests of our Nb₂O₅-based sensor reveal excellent reliability which is of particular importance for application as resistive sensors for a variety gases.     

Temperature dependent H2S and Cl2 sensing selectivity of Cr2O3 thin films

The conductometric gas sensing characteristics of Cr₂O₃ thin films - prepared by electron-beam deposition of Cr films on quartz substrate followed by oxygen annealing - have been investigated for a host of gases (CH₄, CO, NO₂, Cl₂, NH₃ and H₂S) as a function of operating temperature (between 30 and 300 °C) and gas concentration (1-30 ppm). We demonstrate that these films are highly selective to H₂S at an operating temperature of 100 °C, while at 220 °C the films become selective to Cl₂. This result has been explained on the basis of depletion of chemisorbed oxygen from the surface of films due to temperature and/or interaction with Cl₂/H₂S, which is supported experimentally by carrying out the work function measurements using Kelvin probe method. The temperature dependent selectivity of Cr₂O₃ thin films provides a flexibility to use same film for the sensing of Cl₂ as well as H₂S.     

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.     

Synthesis of Bi and Gd doped ZnB2O4 for evaluation as potential materials in luminescent display applications

A series of Bi³⁺ and Gd³⁺ doped ZnB₂O₄ phosphors were synthesized with solid state reaction technique. X-ray diffraction technique was employed to study the structure of prepared samples. Excitation and emission spectra were recorded to investigate the luminescence properties of phosphors. The doping of Bi³⁺ or Gd³⁺ with a small amount (no more than 3 mol%) does not change the structure of prepared samples remarkably. Bi³⁺ in ZnB₂O₄ can emit intense broad-band purplish blue light peaking at 428 nm under the excitation of a broad-band peaking at 329 nm. The optimal doping concentration of Bi³⁺ is experimentally ascertained to be 0.5 mol%. The decay time of Bi³⁺ in ZnB₂O₄ changes from 0.88 to 1.69 ms. Gd³⁺ in ZnB₂O₄ can be excited with 254 nm ultraviolet light and yield intense 312 nm emission. The optimal doping concentration of Gd³⁺ is experimentally ascertained to be 5 mol%. The decay time of Gd³⁺ in ZnB₂O₄ changes from 0.42 to 1.36 ms.     

Mechanism of CO and O3 sensing on WO3 surfaces: First principle study

The microscopic mechanism of O₃ and CO sensing on WO₃ surfaces is clarified by a first principle study. It is shown that ozone reduces to O₂ on the (0 0 1) surface of WO₃ decreasing in such a way the number of oxygen vacancies and the conductivity (since oxygen vacancies act as donors in WO₃). The mechanism of CO sensing is just the opposite: the CO molecule is oxidized to CO₂ on the WO₃ surface increasing the number of oxygen vacancies and the conductivity. The reaction enthalpy for the reduction process of O₃ is found to be −2.54 eV in local density approximation (LDA) and −2.86 in generalized gradient approximation (GGA). The corresponding values for CO are −1.73 eV (LDA) and −1.52 eV (GGA). The adsorptions of O₃ and CO without reduction or oxidation are also calculated but the related energies are much smaller.     

A technique for monitoring SO2 in combustion exhausts: Use of a non-Nernstian sensing element in combination with an upstream catalytic filter

Detection of sulfur dioxide (SO₂) at high temperature (600–750 °C) in the presence of some interferents found in combustion exhausts (NO₂, NO, CO₂, CO, and hydrocarbon (C₃H₆)) is described. The detection scheme involves use of a catalytic filter in front of a non-Nernstian (mixed-potential) sensing element. The catalytic filter was a Ni:Cr powder bed operating at 850 °C, and the sensing elements were pairs of platinum (Pt) and oxide (Ba-promoted copper chromite ((Ba,Cu)_xCr_yO_z) or Sr-modified lanthanum ferrite (LSF)) electrodes on yttria-stabilized zirconia. The Ni:Cr powder bed was capable of reducing the sensing element response to NO₂, NO, CO, and C₃H₆, but the presence of NO₂ or NO (“NO_x”, at 100 ppm by volume) still interfered with the SO₂ response of the Pt–(Ba,Cu)_xCr_yO_z sensing element at 600 °C, causing approximately a 7 mV (20%) reduction in the response to 120 ppm SO₂ and a response equivalent to about 20 ppm SO₂ in the absence of SO₂. The Pt–LSF sensing element, operated at 750 °C, did not suffer from this NO_x interference but at the cost of a reduced SO₂ response magnitude (120 ppm SO₂ yielded 10 mV, in contrast to 30 mV for the Pt-(Ba,Cu)_xCr_yO_z sensing element). The powder bed and Pt–LSF sensing element were operated continuously over approximately 350 h, and the response to SO₂ drifted downward by about 7%, with most of this change occurring during the initial 100 h of operation.     

Influence of doping BiYO3 and Nb2O5 on PTCR characteristics of BaTiO3 thermistor ceramics

Nb₂O₅-doped (1 − x)Ba_0.96Ca_0.04TiO₃-xBiYO₃ (where x = 0.01, 0.02, 0.03 and 0.04) lead-free PTC thermistor ceramics were prepared by a conventional solid state reaction method. X-ray diffraction, scanning electron microscope, Agilent E4980A and resistivity-temperature measurement instrument, were used to characteristic the lattice distortion, microstructure, temperature dependence of permittivity and resitivity-temperature dependence. It was revealed that the tetragonality c/a of the perovskite lattice, the microstructure and the Curie temperature changed with the BiYO₃ content. In order to decrease the room temperature resistivity, the effect of Nb₂O₅ on the room temperature resistivity was also studied, and its optimal doping content was finally chosen as 0.2 mol%. The 0.97Ba_0.96Ca_0.04TiO₃-0.03BiYO₃-0.002Nb₂O₅ thermistor ceramic exhibited a low ρ_RT of 3.98 × 10³ Ω cm, a typical PTCR effect of ρ_max/ρ_min > 10³ and a T_c of 153 °C.     

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.     

Synthesis of nearly monodisperse Co3O4 nanocubes via a microwave-assisted solvothermal process and their gas sensing properties

Nearly monodisperse Co₃O₄ nanocubes have been prepared by a microwave-assisted solvothermal (MS) method at 180 °C for 20 min. The samples are characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The XRD pattern and TEM images of the products illustrated that Co₃O₄ nanocubes had a cubic phase with a lateral size of ∼20 nm. The gas response of the Co₃O₄ nanocubes was studied to several typical organic gases. The Co₃O₄ nanocubes showed good gas sensing performance towards xylene and ethanol vapors with rapid and high responses at a low-operating temperature. The results showed that the Co₃O₄ nanocubes can be used to fabricate high performance gas sensors.     

Ab initio calculations of NO2 and SO2 chemisorption onto non-polar ZnO surfaces

The authors present an ab initio study of NO₂ and SO₂ chemisorption onto non-polar ZnO and ZnO surfaces with the aim of providing theoretical hints for further developments in gas sensors. From first principles calculations (DFT-GGA approximation), the most relevant surface reduction scenarios are analyzed and, subsequently, considered in the chemisorption study. First, calculations indicate that NO₂ adsorbs avidly onto Zn surface atoms. This is compatible with the oxidizing character of NO₂. Second, results also explain the sensor poisoning by SO₂ adsorption (since this molecule competes with NO₂ for the same adsorption sites) and indicate that poisoning can only be reverted at typical operation temperatures (T ≤ 700 °C) in the case of stoichiometric ZnO surfaces.     

Electrical response of Sm2O3-doped SnO2 to C2H2 and effect of humidity interference

Pure and Sm₂O₃-doped SnO₂ are prepared through a sol–gel method and characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The sensor based on 6 wt% Sm₂O₃-doped SnO₂ displays superior response at an operating temperature of 180 °C, and the response magnitude to 1000 ppm C₂H₂ can reach 63.8, which is 16.8 times larger than that of pure SnO₂. This sensor also shows high sensitivity under various humidity conditions. These results make our product be a good candidate in fabricating C₂H₂ sensors.     

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.     

Improved crystalline structure and H2S sensing performance of CuO-Au-SnO2 thin film using SiO2 additive concentration

In situ SiO₂-doped SnO₂ thin films were successfully prepared by liquid phase deposition. The influence of SiO₂ additive as an inhibitor on the surface morphology and the grain size for the thin film has been investigated. These results show that the morphology of SnO₂ film changes significantly by increasing the concentration of H₂SiF₆ solution which decreases the grain size of SnO₂. The stoichiometric analysis of Si content in the SnO₂ film prepared from various Si/Sn molar ratios has also been estimated. For the sensing performance of H₂S gas, the SiO₂-doped Cu-Au-SnO₂ sensor presents better sensitivity to H₂S gas compared with Cu-Au-SnO₂ sensor due to the fact that the distribution of SiO₂ particles in grain boundaries of nano-crystallines SnO₂ inhibited the grain growth (<6 nm) and formed a porous film. By increasing the Si/Sn molar ratio, the SiO₂-doped Cu-Au-SnO₂ gas sensors (Si/Sn = 0.5) exhibit a good sensitivity (S = 67), a short response time (t_90% < 3 s) and a good gas concentration characteristic (α = 0.6074). Consequently, the improvement of the nano-crystalline structures and high sensitivity for sensing films can be achieved by introducing SiO₂ additive into the SnO₂ film prepared by LPD method.